BR112021007505A2 - hydrolyzable ethylene silane copolymer, humidification crosslinkable polymer composition, cable, and method for forming a humidification crosslinkable polymer composition - Google Patents

Abstract

HYDROLYZABLE ETHYLENE SILANA COPOLYMER, MOISTURE-CRICKLED POLYMER COMPOSITION, CABLE, AND METHOD FOR FORMING A MOISTURE-RETICULABLE POLYMER COMPOSITION. It is a copolymer of hydrolysable ethylene and silane which includes from 0.1% by weight to 5.0% by weight of hydrolysable silane groups and has a Mz(abs)/Mw(abs) less than or equal to 9.5 ; a ratio of Mz(abs)/Mw(abs) for polydispersity less than or equal to 1.5; polydispersity of 6.6 or greater; a Density x Polydispersity of 6.0 or greater; or an Amorphous Content at Room Temperature x Polydispersity of 360 or greater. Methods of forming a crosslinkable polymer composition by humidification include forming a copolymer of ethylene and hydrolyzable silane at a polymerization temperature greater than or equal to 180°C to less than or equal to 400°C at a pressure of 5,000 psi (34.5 MPa) at 50,000 psi (344.7 MPa); and adding a silanol condensation catalyst to the copolymer of ethylene and hydrolyzable silane.

Description

1 / 54 HYDROLYZABLE ETHYLENE AND SILAN COPOLYMER, POLYMER COMPOSITION RETICULABLE BY MOISTURE, CABLE, AND METHOD TO FORM A COMPOSITION OF

HUMIDIFICATION RETICULABLE POLYMER CROSS REFERENCE TO RELATED ORDERS

[001] This application claims priority from Provisional Patent Application number US 62/758,739 filed November 12, 2018, the entire disclosure of which is incorporated herein by reference.

BACKGROUND FIELD

[002] The present specification generally refers to a fast-wet crosslinking copolymer of hydrolyzable ethylene and silane. In particular, this specification relates to ethylene hydrolyzable silane rapid wetting crosslinking reactor copolymers. This specification is particularly concerned with ethylene hydrolyzable silane rapid wetting crosslinking reactor copolymers which are manufactured without the use of a chain transfer agent.

TECHNICAL BACKGROUND

[003] Ethylene silane copolymers that are made in tubular reactors are routinely used in wetted crosslinkable polymer compositions (generally in combination with silanol condensation catalysts) to manufacture articles such as low voltage cable constructions. In certain applications, polymer compositions serve as jackets or electrical insulation. Some humidification crosslinkable ethylene silane copolymers include "autoclave-made" ethylene silane copolymers. A chain transfer agent (such as propylene) is known to be used in the production of ethylene silane copolymers in tube reactors and/or autoclaves. Copolymers produced in an autoclave

2/54 are not generally practiced commercially for making crosslinkable polymer compositions with humidification. Alternative wetting crosslinkable copolymers and methods of making such wetting crosslinkable copolymers are desired, especially to produce faster crosslinking.

SUMMARY

[004] According to an embodiment of the present disclosure, a copolymer of ethylene and hydrolyzable silane comprises one or both of 0.1% by weight to 5.0% by weight of hydrolyzable silane groups and from 0.02% by weight to 1.00 mol% of hydrolysable silane groups and has at least one of the following properties: a Mz(abs)/Mw(abs) less than or equal to 9.5; a ratio of "Mz(abs)/Mw(abs)" for polydispersity less than or equal to 1.5; polydispersity of 6.6 or greater; a “Density x Polydispersity” of 6.0 or greater; or an “Ambient Temperature Amorphous Content x Polydispersity” of 360 or greater.

[005] The embodiments of the present disclosure include a polymeric composition crosslinkable by humidification comprising: a copolymer of ethylene and hydrolyzable silane comprising one or both of 0.1% by weight to 5.0% by weight of hydrolyzable silane groups and of 0.02% by mol to 1.00% by mol of hydrolysable silane groups and has at least one of the following properties: a Mz(abs)/Mw(abs) less than or equal to 9.5; a ratio of "Mz(abs)/Mw(abs)" for polydispersity less than or equal to 1.5; polydispersity of 6.6 or greater; a “Density x Polydispersity” of 6.0 or greater; or an “Ambient Temperature Amorphous Content x Polydispersity” of 360 or greater; and a silanol condensation catalyst.

[006] In one embodiment, the polymer composition crosslinkable by humidification has a hot creep, measured at 0.2 MPa and 150 °C or 200 °C in extruded tape with a thickness of 50 mil (1.270 mm) to 80 mil

3 / 54 (2.032 mm), or less than or equal to 100% in 15 days or less than or equal to 80% in 23 days, in which the tape produced from the crosslinkable polymer composition by humidification was cured at 23°C and 50% humidity relative.

[007] According to one or more modalities, the polymer composition crosslinkable by humidification has a hot creep, measured at 0.2 MPa and 150 °C or 200 °C in extruded tape with a thickness of 30 mil (0.762 mm) to 80 mil (2.032 mm), less than or equal to 175% after curing the tape for 4 hours to 20 hours in a water bath at 90 ºC.

[008] The embodiments disclosed in this document include a cable comprising: a conductor; and a jacket or insulation annularly encompassing the conductor, wherein the jacket or insulation comprises a wetting crosslinkable polymeric composition comprising: a copolymer of ethylene and hydrolyzable silane comprising one or both of 0.1% by weight to 5.0% by weight of hydrolysable silane groups and from 0.02 mol% to 1.00 mol% of hydrolysable silane groups and has at least one of the following properties: a Mz(abs)/Mw(abs) less than or equal to 9, 5; a ratio of "Mz(abs)/Mw(abs)" for polydispersity less than or equal to 1.5; polydispersity of 6.6 or greater; a “Density x Polydispersity” of 6.0 or greater; or an “Ambient Temperature Amorphous Content x Polydispersity” of 360 or greater; and a silanol condensation catalyst.

[009] The modalities include a method for forming a crosslinkable polymer composition by humidification comprising: forming a copolymer of ethylene and hydrolyzable silane at a polymerization temperature greater than or equal to 180 °C to less than or equal to 400 °C at a pressure of 5,000 psi (34.5 MPa) to 50,000 psi (344.7 MPa) with or without a chain transfer agent; and adding a silanol condensation catalyst to the copolymer of ethylene and hydrolyzable silane groups.

[0010] Additional features and advantages of the modalities will be

4 / 54 set out in the detailed description below, and in part will be readily apparent to those skilled in the art from such description or recognized for practicing the modalities described herein, including the following detailed description and claims.

[0011] It is to be understood that both the above general description and the following detailed description describe various embodiments and are intended to provide an overview or framework for understanding the nature and character of the claimed matter.

DETAILED DESCRIPTION

[0012] Reference will now be made in detail to modalities of copolymers of ethylene and hydrolyzable silane, methods for making such copolymers, wetting crosslinkable polymeric compositions comprising such copolymers, and products including such wetting crosslinkable compositions. Below are definitions of the terms that are used in this disclosure.

DEFINITIONS

[0013] The numerical ranges disclosed herein include all values of, and including, lower and upper value, unless otherwise specified (such as by the use of "greater than", "less than" or the like. For ranges that contain explicit values (for example, 1 or 2; or 3 to 5; or 6; or 7), any subrange between two explicit values is included (for example, 1 to 2; 2 to 6; 5 to 7; 3 to 7; 5 to 6; etc.).

[0014] Unless otherwise indicated, implied from the context or customary in the art, all parts and percentages are based on weight and all test methods are current as of the filing date of this disclosure.

[0015] "Composition" and similar terms mean a mixture of materials that comprise the composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0016] "Polymer" and similar terms mean a compound

5 / 54 macromolecular prepared by reacting (ie polymerizing) monomers of the same or different type. "Polymer" includes homopolymers and interpolymers. Quantities of trace impurities, for example catalyst residues, can be incorporated into and/or within the polymer. The term also encompasses all forms of copolymer, eg random, block etc. Although a polymer is often referred to as being "produced from" one or more specified monomers, "based on" a specified monomer or type of monomer, "containing" a specified monomer content, or the like in that context, the term "monomer" is understood to refer to the polymerized remainder of the specified monomer and not to the unpolymerized species. In general, polymers are mentioned as being based on "units" which are the polymerized form of a corresponding monomer.

[0017] "Interpolymer" means a polymer prepared by polymerizing at least two different monomers. This generic term includes copolymers, commonly used to refer to polymers made from different monomers and made from more than two different monomers, eg terpolymers, tetrapolymers, etc.

[0018] "Polyolefin", "PO" and similar terms mean a polymer derived from simple olefins. Many polyolefins are thermoplastic and, for purposes of this disclosure, can include a rubber phase. Representative polyolefins include polyethylene, polypropylene, polybutene, polyisoprene and their various interpolymers.

[0019] "Ethylene polymer", "ethylene-based polymer", "ethylene polymer", "polyethylene", "ethylene" and similar terms mean a polymer containing equal to or greater than 50 percent by weight (% by weight ) or a major amount of polymerized ethylene based on the weight of polymer and optionally may comprise one or more polymerized comonomers. The generic term "ethylene-based polymer" includes,

6/54 mode, the ethylene homopolymer and the ethylene interpolymer. Ethylene-based polymers include copolymers of ethylene and hydrolyzable silanes.

[0020] A "conductor" is an elongated shaped element (wire, cable, optical fiber) to transfer energy at any voltage (DC, AC or transient). The conductor is typically at least a metal wire or at least a metal cable (such as aluminum or copper), but it can be fiber optics. The conductor can be a single cable or a plurality of cables connected together (i.e., a cable core or a core).

[0021] A "sheath" is a generic term and, when used in relation to cables, includes coverings or layers of insulation, protective jackets and the like.

[0022] A "wire" means a single strand of conductive metal, eg copper or aluminum, or a single strand of optical fiber.

[0023] A "cable" and similar terms mean at least one conductor, eg wire, optical fiber, etc., within a protective jacket or sheath. Typically, a cable is formed from two or more strands or two or more optical fibers joined together in a common protective jacket or sheath. Combined cables can contain both electrical wires and optical fibers. The individual strands or fibers within the jacket or sheath may be exposed, covered or insulated. Typical cable designs are illustrated in US Patent Nos. 5,246,783; 6,496,629; and 6,714,707, each of which is incorporated herein by reference in its entirety.

[0024] "Cross-linkable", "curable" and similar terms mean that the polymer, before or after it is formed into an article, is not cured or cross-linked and has not been subjected to or exposed to treatment that has induced substantial cross-linking, although the polymer comprises additive (or additives) or functionality that will cause, promote or permit substantial crosslinking upon subjection or exposure to such treatment (eg, exposure to water).

7/54

"Wet crosslinkable polymer composition" and similar terms mean a composition comprising a polymer that can be crosslinked upon exposure to humidification or water at an appropriate temperature. In embodiments, one of the polymers in the composition has hydrolyzable silane groups.

[0026] "Hydrolyzable silane group" and similar terms mean a silane group that will react with water. These include alkoxysilane groups on monomers or polymers that can hydrolyze to produce silanol groups, which, in turn, can condense to crosslink the monomers or polymers.

[0027] “Ambient temperature” and similar terms mean 23°C ± 2°C.

[0028] “Ambient conditions” and similar terms mean ambient temperature and relative humidity” (ranging from 10% to 100%).

[0029] It is also to be understood that, as used herein, hydrolyzable silanes include hydrolyzable silanes that can be copolymerized with ethylene, such as olefinically functional hydrolysable silanes, olefinically unsaturated hydrolysable silanes or hydrolysable silanes with alkenyl functionality.

HYDROLYZABLE ETHYLENE AND SILANA COPOLYMER

[0030] Surprisingly, it has been found that copolymers of ethylene and hydrolyzable silane have at least one of the following properties: an Mz(abs)/Mw(abs) less than or equal to 9.5; a ratio of "Mz(abs)/Mw(abs)" for polydispersity less than or equal to 1.5; polydispersity of 6.6 or greater; a “Density x Polydispersity” of 6.0 or greater; or an “Ambient Temperature Amorphous Content x Polydispersity” of 360 or more is crosslinked considerably faster at ambient conditions than those that do not meet these criteria. Non-limiting examples of copolymers of ethylene and silane hydrolyzable with

8/54 at least one of the following properties: a Mz(abs)/Mw(abs) less than or equal to 9.5; a ratio of "Mz(abs)/Mw(abs)" for polydispersity less than or equal to 1.5; polydispersity of 6.6 or greater; a “Density x Polydispersity” of 6.0 or greater; or an “Ambient Temperature Amorphous Content x Polydispersity” of 360 or more was produced in an autoclave reactor at a polymerization temperature of 250 °C without employing a chain transfer agent. Humidification crosslinkable hydrolyzable ethylene silane copolymers having at least one of the following properties: a Mz(abs)/Mw(abs) less than or equal to 9.5; a ratio of "Mz(abs)/Mw(abs)" for polydispersity less than or equal to 1.5; polydispersity of 6.6 or greater; a “Density x Polydispersity” of 6.0 or greater; or an "Ambient Temperature Amorphous Content x Polydispersity" of 360 or greater may exhibit molecular weight distributions that allow hydrolysable ethylene silane copolymers to rapidly cross-link under ambient conditions (such as ambient temperature and relative humidity) in presence of a silanol condensation catalyst.

[0031] Accordingly, in one embodiment, a copolymer of ethylene and hydrolyzable silane comprises from 0.1% by weight to 5.0% by weight of hydrolyzable silane groups and has at least one of the following properties: an Mz(abs)/ Mw(abs) less than or equal to 9.5; a ratio of "Mz(abs)/Mw(abs)" for polydispersity less than or equal to 1.5; polydispersity of 6.6 or greater; a “Density x Polydispersity” of 6.0 or greater; or an “Ambient Temperature Amorphous Content x Polydispersity” of 360 or greater. In some embodiments, the hydrolyzable ethylene silane copolymer comprises from 0.2% by weight to 5.0% by weight of hydrolyzable silane groups, such as from 0.4% by weight to 5.0% by weight of hydrolyzable silane groups , from 0.6% by weight to 5.0% by weight of hydrolyzable silane groups, from 0.8% by weight to 5.0% by weight of silane groups

9/54 hydrolysables, from 1.0% by weight to 5.0% by weight of hydrolysable silane groups, from 1.2% by weight to 5.0% by weight of hydrolysable silane groups, from 1.4% by weight to 5.0% by weight of hydrolyzable silane groups, from 1.8% by weight to 5.0% by weight of hydrolyzable silane groups, from 2.0% by weight to 5.0% by weight of hydrolyzable silane groups, from 2.2% by weight to 5.0% by weight of hydrolyzable silane groups, from 2.4% by weight to 5.0% by weight of hydrolysable silane groups, from 2.6% by weight to 5.0% by weight of hydrolyzable silane groups, from 2.8% by weight to 5.0% by weight of hydrolysable silane groups, from 3.0% by weight to 5.0% by weight of hydrolyzable silane groups, from 3.0% by weight to 5.0% by weight of hydrolyzable silane groups, from 3.2% by weight to 5.0% by weight of hydrolyzable silane groups, from 3.4% by weight to 5.0% by weight of silane groups hydrolysables, from 3.6% by weight to 5.0% by weight hydrolysable silane groups, from 3.8% by weight to 5.0% by weight of hydrolysable silane groups, from 4.0% by weight to 5.0 % by weight of hydrolyzable silane groups, from 4.2% by weight to 5.0% by weight of hydrolyzable silane groups, from 4.4% by weight to 5.0% by weight of hydrolyzable silane groups, from 4.6% by weight to 5.0% by weight of hydrolysable silane groups, or from 4.8% by weight to 5.0% by weight of hydrolysable silane groups.

In some embodiments, the hydrolyzable ethylene silane copolymer comprises from 0.1% by weight to 4.8% by weight of hydrolyzable silane groups, such as from 0.1% by weight to 4.6% by weight of hydrolyzable silane groups from 0.1% by weight to 4.4% by weight of hydrolyzable silane groups, from 0.1% by weight to 4.2% by weight of hydrolysable silane groups, from 0.1% by weight to 4.0 % by weight of hydrolysable silane groups, from 0.1% by weight to 3.8% by weight of hydrolysable silane groups, from 0.1% by weight to 3.6% by weight of hydrolysable silane groups, from 0.1 % by weight to 3.4% by weight of hydrolyzable silane groups, from 0.1% by weight to 3.2% by weight of silane groups

10 / 54 hydrolysables, from 0.1% by weight to 3.0% by weight of hydrolysable silane groups, from 0.1% by weight to 2.8% by weight of hydrolysable silane groups, from 0.1% by weight to 2.6% by weight of hydrolysable silane groups, from 0.1% by weight to 2.4% by weight of hydrolysable silane groups, from 0.1% by weight to 2.2% by weight of hydrolysable silane groups, from 0.1% by weight to 2.0% by weight of hydrolyzable silane groups, from 0.1% by weight to 1.8% by weight of hydrolysable silane groups, from 0.1% by weight to 1.6% by weight of hydrolyzable silane groups, from 0.1% by weight to 1.4% by weight of hydrolysable silane groups, from 0.1% by weight to 1.2% by weight of hydrolysable silane groups, from 0.1% by weight to 1.0% by weight of hydrolyzable silane groups, from 0.1% by weight to 0.8% by weight of hydrolyzable silane groups, from 0.1% by weight to 0.6% by weight of hydrolyzable silane groups, from 0.1% by weight to 0.4% by weight of hydrolysable silane groups, or from 0.1% by weight to 0.2% by weight of hydrolysable silane groups. In some embodiments, the hydrolyzable ethylene silane copolymer comprises from 0.9% by weight to 3.5% by weight of hydrolyzable silane groups, such as from 1.1% by weight to 3.0% by weight of hydrolyzable silane groups or from 1.3% by weight to 2.5% by weight of hydrolysable silane groups.

[0032] In some embodiments, the copolymer of ethylene and hydrolyzable silane comprises from 0.02% by mole to 1.00% by mole of hydrolyzable silane groups, such as from 0.17% by mole to 0.68% by mole of hydrolyzable silane groups, or from 0.23% by mol to 0.37% by mol of hydrolysable silane groups, or from 0.25% by mol to 0.38% by mol of hydrolysable silane groups, or by 0.38% in mol to 1.00 mol% of hydrolysable silane groups, or from 0.38 mol% to 0.68 mol% of hydrolysable silane groups.

[0033] In some embodiments, the hydrolyzable ethylene-silane copolymer comprises from 0.01 mol/kg to 0.34 mol/kg of silane groups

11 / 54 hydrolyzable, such as from 0.06 mol/kg to 0.24 mol/kg of hydrolyzable silane groups, or from 0.08 mol/kg to 0.13 mol/kg of hydrolyzable silane groups, or from 0. 09 mol/kg to 0.14 mol/kg of hydrolysable silane groups, or from 0.14 mol/kg to 0.34 mol/kg of hydrolysable silane groups, or from 0.14 mol/kg to 0.24 mol/kg of hydrolyzable silane groups.

[0034] In some embodiments, the content of long-chain branching (LCB; C6 and greater per 1,000 carbon atoms) is 2.9 or greater, or 3.0 or greater, or 3.1 or greater, or 3, 2 or higher, or 3.3 or higher, or 3.4 or higher, or 3.5 or higher.

[0035] In some embodiments, the copolymer of ethylene and hydrolyzable silane has a polydispersity greater than 2.0, such as greater than 2.5, greater than 3.0, greater than 3.5, greater than 4.0, greater than 4.5, greater than 5.0, greater than 5.5, greater than 5.9, greater than 6.0, greater than 6.1, greater than 6.2, greater than 6.3, greater than 6, 4, greater than 6.5, greater than 6.6, greater than 6.7, greater than 6.8, greater than 6.9, greater than 7.0, greater than 7.5, greater than 8.0, greater than 8.5 or greater than 9.0. In some embodiments, the maximum polydispersity is 15.0, 13.0 or 10.0. Consequently, in some embodiments, the hydrolyzable ethylene silane copolymer has a polydispersity greater than 2.0 to 15.0, such as greater than 3.0 to 15.0, greater than 4.0 to 15.0, greater than 4 .5 to 15.0, greater than 5.0 to 15.0, greater than 5.5 to 15.0, greater than 6.0 to 15.0, greater than 6.1 to 15.0, from greater than 6.2 to 15.0, from greater than 6.3 to 15.0, from greater than 6.4 to 15.0, from greater than 6.5 to 15.0, from greater than 6.6 to 15.0, from greater than 6.7 to 15.0, from greater than 6.8 to 15.0, from greater than 6.9 to 15.0, from greater than 7.0 to 15.0, from greater than 7.5 to 15.0, greater than 8.0 to 15.0, greater than 8.5 to 15.0, or greater than 9.0 to 15.0.

[0036] In some embodiments, the hydrolyzable ethylene silane copolymer has a Mz(abs)/Mw(abs) less than or equal to 9.5, or less than or equal to 9.0, or less than or equal to 8.5 , or less than or equal to 8.0, or less than or equal to 7.5, or less than or equal to 7.0, or less than or equal to 6.5, or less than or

12 / 54 equal to 6.0, or less than or equal to 5.5, or less than or equal to 5.0.

[0037] In some embodiments, the hydrolyzable ethylene silane copolymer has a ratio of "Mz(abs)/Mw(abs)" for polydispersity less than or equal to 1.5, or less than or equal to 1.4, or less or equal to 1.3, or less than or equal to 1.2, or less than or equal to 1.1, or less than or equal to 1.0, or less than or equal to 0.9, or less than or equal to 0, 8, or less than or equal to 0.7, or less than or equal to 0.6.

[0038] According to the modalities, the copolymer of ethylene and hydrolyzable silane has a melt index (I2 in g/10 min) from 0.1 to 30, such as from 0.2 to 25, from 0.3 to 20 , from 0.4 to 15.0, from 0.5 to 10.0, from 0.6 to 8.0, from 0.7 to 6.0, from 0.8 to 5.0, from 0.9 to 4.0, from 1.0 to 3.5, from 1.1 to 3.3, from 1.2 to 3.1, from 1.3 to 2.9, from 1.4 to 2.7, from 1.5 to 2.5, from 1.6 to 2.3 or from 1.7 to 2.1. In some embodiments, the hydrolyzable ethylene silane copolymer has an I2 from 0.8 to 3.6, such as from 0.8 to 3.3, from 0.8 to 3.1, from 0.8 to 2.9 , from 0.8 to 2.7, from 0.8 to 2.5, from 0.8 to 2.3, from 0.8 to 2.1, from 0.8 to 2.0, from 0.8 to 1.9, from 0.8 to 1.8, from 0.8 to 1.7, from 0.8 to 1.6, from 0.8 to 1.5, from 0.8 to 1.4, or from 0.8 to 1.3. I2 is determined under ASTM D-1238, Condition E and measured at 190°C and 2.16 kg.

[0039] In embodiments, the hydrolyzable ethylene-silane copolymer has a density (g/cm³) of 0.910 g/cm³ to 0.970 g/cm³, such as from 0.911 g/cm³ to 0.960 g/cm³, from 0.912 g/cm³ to 0.950 g/cm³, from 0.913 g/cm³ to 0.940 g/cm³, from 0.913 g/cm³ to 0.930 g/cm³, from 0.913 g/cm³ to 0.925 g/cm³, from 0.913 g/cm³ to 0.925 g/cm³, or from 0.913 g/cm³ to 0.923 g/cm³, or from 0.913 g/cm³ to 0.922 g/cm³, or from 0.913 g/cm³ to 0.921 g/cm³, or from 0.913 g/cm³ to 0.920 g/cm³, or from 0.913 g/cm³ to 0.919 g/cm³, or from 0.913 g/cm³ to 0.918 g/cm³, or from 0.913 g/cm³ to 0.917 g/cm³, or from 0.913 g/cm³ to 0.916 g/cm³, or 0.913 g /cm³ to 0.915 g/cm³. In one embodiment, the hydrolyzable ethylene silane copolymer has a density less than 0.923 g/cm³, or less than 0.922 g/cm³, or less than 0.921 g/cm³, or less than 0.920 g/cm³, or less than 0.919 g /cm³, or less than 0.918 g/cm³, or less than 0.917 g/cm³, or less

13 / 54 than 0.916 g/cm³. Density is measured in accordance with ASTM D-792.

[0040] In embodiments, the room temperature crystallinity (% by weight) of the hydrolyzable ethylene silane copolymer ranges from 5% by weight to 65% by weight, such as from 10% by weight to 60% by weight, from 15% by weight to 55% by weight, from 20% by weight to 50% by weight, from 25% by weight to 50% by weight, from 30% by weight to 50% by weight, from 35% by weight to 50% by weight weight, from 40% by weight to 50% by weight, from 41% by weight to 50% by weight, 42% by weight to 50% by weight, from 43% by weight to 50% by weight, from 44% by weight to 51% by weight, from 45% by weight to 50% by weight, from 46% by weight to 50% by weight, from 47% by weight to 50% by weight, from 48% by weight to 50% by weight. In embodiments, the hydrolyzable ethylene silane copolymer has a crystallinity at room temperature less than 50% by weight, or less than 49% by weight, or less than 48% by weight, or less than 47% by weight, or less than 46% by weight, or less than 45% by weight, or less than 44% by weight, or less than 42% by weight, or less than 40% by weight, or less than 38% by weight, or less than 36% by weight, or less than 34% by weight, or less than 32% by weight, or less than 30% by weight, or less than 25% by weight, or less than 20% by weight, or less than 15% by weight . Crystallinity is measured as described in the Examples.

[0041] In embodiments, the amorphous content at room temperature (% by weight) of the copolymer of ethylene hydrolyzable silane ranges from 95% by weight to 35% by weight, such as from 90% by weight to 40% by weight, from 85 % by weight to 45% by weight, from 80% by weight to 50% by weight, from 75% by weight to 50% by weight, from 70% by weight to 50% by weight, from 65% by weight to 50% by weight, from 60% by weight to 50% by weight, from 59% by weight to 50% by weight, 58% by weight to 50% by weight, from 57% by weight to 50% by weight, from 56% by weight weight to 51% by weight, from 55% by weight to 50% by weight, from 54% by weight to 50% by weight, from 53% by weight to 50% by weight, from 52% by weight to 50% by weight . In embodiments, the hydrolyzable silane ethylene copolymer has an amorphous content at temperature

14 / 54 environment 50% by weight or more, 51% by weight or more, or 52% by weight or more, or 53% by weight or more, or 54% by weight or more, or 55% by weight or more , or 56% by weight or more, or 58% by weight or more, or 60% by weight or more, or 62% by weight or more, or 64% by weight or more, or 66% by weight or more, or 68% by weight or more, or 70% by weight or more, or 75% by weight or more, or 80% by weight or more, or 85% by weight or more. The amorphous content at room temperature is calculated as "100% by weight minus crystallinity at room temperature (% by weight)".

[0042] In embodiments, the hydrolyzable ethylene silane copolymer has a polydispersity and density product (i.e., "Density x Polydispersity" or "Density x Mw (conv)/Mn (conv)") of 6.0 or greater , or 6.1 or higher, or 6.3 or higher, or 6.5 or higher, or 6.7 or higher, or 6.9 or higher, or 7.1 or higher, or 7.5 or higher, or 8.0 or greater or 8.5 or greater, or 9.0 or greater, or 9.5 or greater, or 10.0 or greater.

[0043] In embodiments, the hydrolyzable ethylene-silane copolymer has a product of polydispersity and amorphous content at room temperature (ie, "Amorphous Content at Room Temperature x Polydispersity" or "Amorphous Content at Room Temperature x Mw(conv)/ Mn(conv)") of 355 or more, or 360 or more, or 370 or more, or 380 or more, or 390 or more, or 400 or more, or 410 or more, or 420 or more, or 430 or more , or 440 or more, or 450 or more, or 460 or more, or 470 or more, or 480 or more.

[0044] In embodiments, the hydrolyzable ethylene silane copolymer has an LCB product, polydispersion and amorphous content at room temperature (i.e. "Amorphous Content at Room Temperature x Polydispersity x LCB") of 1,000 or greater, 1,025 or greater , 1,050 or more, 1,075 or more,

1,100 or more, 1,125 or more, 1,175 or more, 1,200 or more,

1,225 or more, 1,250 or more, 1,275 or more, 1,300 or more,

15/54

1,325 or more, 1,350 or more, 1,375 or more, 1,400 or more,

1,425 or more, 1,450 or more, 1,500 or more, 1,525 or more,

1,550 or more, 1,575 or more, 1,600 or more, 1,700 or more,

1800 or higher, or 1900 or higher.

[0045] In embodiments, the copolymer of ethylene and hydrolyzable silane has terminal vinyls per 1,000 carbon atoms from 0.01 to 1.0, or from 0.01 to 0.5, or from 0.01 to 0.3, or from 0.01 to 0.2, or from 0.01 to 0.1, or from 0.01 to 0.08 or from 0.02 to 0.06 or from 0.03 to 0.05.

[0046] In one embodiment, the hydrolyzable ethylene silane copolymer comprises other units that may be derived from one or more other polymerizable comonomers, including (but not limited to) unsaturated esters, monomeric chain transfer agent (CTA), α- olefins and anhydrides, each typically having no more than 20 carbon atoms. α-Olefin comonomers, which have a combined monomer and CTA functionality, can have 3 to 10 carbon atoms, or alternatively, α-olefin comonomers can have 3 to 8 carbon atoms. Exemplary α-olefin comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-1-pentene and combinations of the same. In embodiments, α-olefin comonomers are selected from propylene, 1-butene and combinations thereof. The unsaturated esters can be alkyl acrylates, alkyl methacrylates or vinyl carboxylates. The alkyl group can have 1 to 8 carbon atoms and preferably 1 to 4 carbon atoms. Carboxylate groups can have 2 to 8 carbon atoms, or 2 to 5 carbon atoms. Examples of acrylates and methacrylates include, but are not limited to, ethyl acrylate, methyl acrylate, methyl methacrylate, t-butyl acrylate, n-butyl acrylate, n-butyl methacrylate and 2-ethylhexyl acrylate. Examples of vinyl carboxylates include, for example, vinyl acetate, vinyl propionate and vinyl butanoate.

16 / 54

[0047] In embodiments, the copolymer of ethylene and hydrolyzable silane contains a "branching agent". Examples of suitable branching agents are those disclosed in International Application number WO 2016204949A1, which is incorporated herein by reference in its entirety.

[0048] According to the modalities, the copolymer of ethylene and hydrolyzable silane can be branched, linear or substantially linear and can be produced by polymerization or copolymerization in a reactor (low pressure or high pressure). As used herein, the term "high pressure reactor" or "high pressure process" is any reactor or process operated at a pressure of at least 5,000 pounds per square inch (psi) (34.47 megaPascal or MPa). “Branched” ethylene polymers are often (but not only) prepared in a high pressure reactor or process and tend to have highly branched polymeric structures, with branches found both in the polymer structure and in the branches themselves. By contrast, "substantially linear" denotes a polymer that has a backbone that is replaced by 0.01 to 3 long chain branches per 1,000 carbon atoms. In some embodiments, the ethylenic polymer can have a backbone that is substituted by 0.01 to 1 long-chain branch per 1,000 carbon atoms, or 0.05 to 1 long-chain branch per 1,000 carbon atoms.

[0049] The copolymer of ethylene and hydrolyzable silane can be used alone or in blends with other polymers, including (but not limited to) ethylene polymers. Ethylene polymers used in the embodiments disclosed and described herein may include homopolymers and interpolymers, random and block and functionalized copolymers (e.g., ethylene vinyl acetate, ethylene ethyl acrylate, etc.) and non-functionalized polymers. Ethylene interpolymers or modalities can include

17 / 54 at least one of elastomers, flexomers and plastomers. The ethylene polymer may, in embodiments, comprise at least 50, such as at least 60, and more, such as at least 80% by weight of ethylene-derived units. The other ethylene interpolymer units can be derived from one or more polymerizable monomers including, for example, α-olefins and unsaturated esters.

[0050] The α-olefin is, in the embodiments, a linear, branched or cyclic C3-C20 α-olefin. Examples of C3-C20 α-olefins include, for example, propene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-octadecene. α-olefins can also contain a cyclic structure such as cyclohexane or cyclopentane, resulting in an α-olefin such as 3-cyclohexyl-1-propene (allyl cyclohexane) and vinyl cyclohexane . For purposes of this disclosure, certain cyclic olefins, such as norbornene and related olefins, particularly 5-ethylidene-2-norbornene, are considered α-olefins and can be used in place of some or all of the α-olefins described above. Accordingly, styrene and its related olefins (eg, α-methylstyrene, etc.) are considered α-olefins for the purposes of this disclosure. In some embodiments, ethylene interpolymers include copolymers of ethylene/propylene, ethylene/butene, ethylene/1-hexene, ethylene/1-octene, ethylene/styrene, and the like. Illustrative ethylenic terpolymers include ethylene/propylene/1-octene, ethylene/propylene-/butene, ethylene/butene/1-octene, ethylene/propylene/diene monomer (EPDM) and ethylene/butene/styrene.

[0051] In various embodiments, unsaturated esters can be alkyl acrylates, alkyl methacrylates, alkyl maleates or vinyl carboxylates. The alkyl group can have 1 to 8 carbon atoms and preferably 1 to 4 carbon atoms. Carboxylate groups can have 2 to 8 carbon atoms, or 2 to 5 carbon atoms. Examples of Acrylates and Methacrylates

18 / 54 include, but are not limited to, ethyl acrylate, methyl acrylate, methyl methacrylate, t-butyl acrylate, n-butyl acrylate, n-butyl methacrylate and 2-ethylhexyl acrylate. Examples of vinyl carboxylates include, for example, vinyl acetate, vinyl propionate and vinyl butanoate. Examples of alkyl maleates include, for example, monoethyl maleate.

[0052] Examples of ethylene polymers used in modalities include, for example, high density polyethylene (HDPE); medium density polyethylene (MDPE); linear low density polyethylene (LLDPE); low density polyethylene (LDPE); very low density polyethylene (VLDPE); homogeneously branched linear ethylene/α-olefin copolymers (for example, TAFMERTM from Mitsui Petrochemicals Company Limited and EXACTTM from DEX-Plastomers); substantially linear, homogeneously branched ethylene/α-olefin polymers (for example, AFFINITYTM polyolefin plastomers and ENGAGETM polyolefin elastomers available from The Dow Chemical Company); and ethylene block copolymers (INFUSETM also available from The Dow Chemical Company). Substantially linear ethylene copolymers are more fully described in US Patent Nos. 5,272,236; 5,278,272; and

5,986,028, and ethylene block copolymers are more fully described in US Patent Nos. 7,579,408; 7,355,089; 7,524,911;

7,514,517; 7,582,716; and 7,504,347, all of which are incorporated herein by reference in their entirety.

[0053] According to the modalities, the hydrolyzable silane can be any silane that will effectively copolymerize with ethylene and thus allow crosslinking of the ethylene polymer. Those hydrolyzable silanes described by the formula below are exemplary comonomer (or exemplary comonomer) that can be used in the embodiments.

19 / 54 where R' is a hydrogen atom or methyl group; x and y are 0 or 1 with the proviso that when x is 1, y is 1; n is an integer from 1 to 12 inclusive, such as 1 to 4, and each R'' is independently a hydrolyzable organic group, such as an alkoxy group having 1 to 12 carbon atoms (eg, methoxy, ethoxy, butoxy) , aryloxy group (eg phenoxy), aryloxy group (eg benzyloxy), aliphatic acyloxy group having 1 to 12 carbon atoms (eg formyloxy, acetyloxy, propanoyloxy), amino or substituted amino groups (alkylamino, arylamino ), or a lower alkyl group having 1 to 6 carbon atoms inclusive, with the proviso that no more than one of the three R" groups is an alkyl.

These hydrolyzable silanes can be copolymerized with ethylene in a reactor, as a high pressure process, to make a copolymer of ethylene and another monomer that has hydrolyzable silane groups.

Suitable hydrolyzable silanes include unsaturated silanes comprising an ethylenically unsaturated hydrocarbyl group such as a vinyl, allyl, isopropenyl, butenyl, cyclohexenyl or gamma-(meth)acryloxyallyl group, and a hydrolyzable group such as, for example, a hydrocarbyloxy, hydrocarbonyloxy. or hydrocarbylamino group.

Examples of hydrolyzable groups include methoxy, ethoxy, formyloxy, acetoxy, propionyloxy and alkyl or arylamino groups.

Hydrolyzable silanes include unsaturated alkoxysilanes that can be copolymerized in the reactor with other monomers (such as ethylene and acrylates). These hydrolyzable silanes and their method of preparation are more fully described in US Patent number 5,266,627, which is incorporated herein by reference in its entirety.

In the embodiments, the hydrolyzable silanes are selected from the group consisting of vinyltrimethoxysilane (VTMS), vinyltriethoxysilane (VTES), 3-methacryloxypropyltrimethoxysilane (M3M), vinyltriacetoxysilane and its

20 / 54 mixes. The amount of hydrolyzable silane used to functionalize the ethylenic polymer can vary widely depending on the nature of the polymer, the silane, the processing or reactor conditions, the copolymerization efficiency, the end application and similar factors, but typically and according to in the modality, at least 0.1 or at least 0.3 or at least 0.5 percent by weight is used. Convenience and economic considerations are two of the main limitations on the maximum amount of hydrolyzable silane used and typically the maximum amount of hydrolyzable silane is less than or equal to 5% by weight, generally less than or equal to 2% by weight.

METHODS FOR FORMING ETHYLENE AND SILAN COPOLYMERS HYDROLYZABLE

[0054] According to the modalities, the copolymer of ethylene and hydrolyzable silane is formed in an autoclave reactor or a tubular reactor or a combination thereof. In embodiments, ethylene and a hydrolyzable silane component - for example, one or more of those described above - are introduced into the reactor, along with the polymerization initiator and, optionally, a chain transfer agent. The amount of hydrolyzable silane component added to the reactor may, in the embodiments, be within the ranges disclosed above.

[0055] To produce the copolymer and hydrolyzable silane, a high pressure free radical initiated polymerization process is typically used. Two different types of high pressure free radical initiated polymerization reactors are known. In one type, an agitated autoclave vessel that has one or more reaction zones is used. The autoclave reactor typically has multiple injection points for initiator and/or monomer feeds. In the second type, a jacketed tube that has one or more reaction zones is used as a reactor. Appropriate but not limited lengths of reactor used accordingly

21 / 54 with the modalities can be from 100 to 3600 meters (m) or from 1,000 to

2800 m. The start of a reaction zone, for any type of reactor, is typically defined by the injection site of the reaction initiator, ethylene, chain transfer agent (CTA, also known as a telomer), comonomer (or comonomer) and any combination of them. Addition points and amounts of fresh ethylene, fresh CTA, fresh comonomer (or fresh comonomer) and fresh branching agent (if any) can be adequately controlled to achieve the desired ratios of CTA to ethylene and comonomer (or comonomer) for ethylene and branching agent for ethylene in feeds to and/or in reaction zones.

[0056] The hydrolyzable ethylene silane copolymer used in the modalities is produced in a reactor configuration comprising at least one tubular reactor and/or at least one autoclave reactor. As used in this disclosure, "reactor configuration" means the type and number of reactors used in the process to make the hydrolyzable ethylene silane copolymer. An autoclave reactor can have one or more reactor zones. A tubular reactor can have one or more reaction zones and a reactor configuration can comprise one or more tubular reactors, each with one or more reaction zones. In one embodiment, the reactor configuration comprises a tubular reactor and an autoclave reactor, and the tubular reactor is downstream of the autoclave reactor.

[0057] Optionally, in some embodiments, a chain transfer agent (CTA) is used to control molecular weight. In embodiments, one or more CTAs are added to the polymerization process. CTAs according to embodiments typically comprise at least one of the following groups: alkanes, aldehydes, ketones, alcohol, ether, esters, mercaptan or phosphine. In embodiments, a CTA comprises at least one group of an alkane, an unsaturated hydrocarbon, a ketone,

22 / 54 an aldehyde, an alcohol or an ether. Under some embodiments, a CTA is selected from the group consisting of saturated hydrocarbons, unsaturated hydrocarbons, ketones, aldehydes, alcohols, ethers, esters, mercaptans or phosphines. Under some embodiments, a CTA is selected from the group consisting of saturated hydrocarbons, unsaturated hydrocarbons, ketones, aldehydes, alcohols, and ethers. Exemplary CTAs include, but are not limited to, propylene, isobutane, n-butane, 1-butene, methyl ethyl ketone, acetone, ethyl acetate, propionaldehyde, ISOPARTM-C, -E and -H (ExxonMobil Chemical Co.) and isopropanol. In one embodiment, the amount of CTA used in the process is from 0.03 to 10 percent by weight of the total reaction mixture. In the modalities, no CTA is added to the polymerization process. In modalities, no separate CTA is added, but the solvent used (if any) for the peroxide mixture can also function or function as CTA.

[0058] In modalities in which CTA is added to the polymerization, the ratio of the concentration of CTA in the feed to the reaction zone i (where i is greater than or equal to 2 and the reaction zone i is downstream of the zone of reaction 1) for the concentration of CTA in the feed to reaction zone 1 is greater than or equal to 1.0, or greater than 1.5 or greater than 2.0.

[0059] In embodiments, the process includes a high-pressure, low-pressure recycling loop to improve ethylene efficiency, since ethylene is only partially converted or consumed by passing through the reactor. Typically, the conversion level per reactor pass is between 12% and 40%, with conversion levels for tubular reactors at the higher end of this range, and conversion levels for autoclave reactors at the lower end of this range.

[0060] Free radical initiators are generally used to produce the copolymers of ethylene and hydrolyzable silane according to the modalities. A free radical initiator as used in this

23 / 54 document, refers to a free radical generated by chemical and/or radiation means. Exemplary free radical initiators include organic peroxides including, but not limited to, cyclic peroxides, diacyl peroxides, dialkyl peroxides, hydroperoxides, peroxycarbonates, peroxydicarbonates, peroxyesters and peroxyketals. Initiators include t-butyl peroxy pivalate, di-t-butyl peroxide, t-butyl peroxyacetate and t-butyl peroxy-2-hexanoate, or mixtures thereof. In embodiments, these organic peroxide initiators are used in an amount of 0.001% by weight to 0.25% by weight, based on the weight of polymerizable monomers.

In embodiments, an initiator is added to at least one reaction zone and the initiator has a half-life temperature in one second greater than 255 °C, or greater than 260 °C. In another embodiment, such initiators are used at a peak polymerization temperature of 200 °C to 400 °C, or 320 °C to 350 °C. In other embodiments, the initiator comprises at least one peroxide group incorporated into a ring structure. Examples of such initiators include, but are not limited to, TRIGONOXTM 301 (3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane) and TRIGONOXTM 311 (3,3,5,7,7 -pentamethyl-1,2,4-trioxepane), both available from Akzo Nobel, and HMCH-4-AL (3,3,6,6,9,9-hexamethyl-1,2,4,5-tetroxonane) available at United Initiators. Other initiators are disclosed in International Publication Numbers WO 02/14379 and WO 01/68723, which are each incorporated herein by reference in their entirety.

[0062] The polymerization initiator can be added to the reactor in the amounts mentioned above. The amount of ethylene component added to the reactor may, in the embodiments, comprise the remainder of the composition introduced into the reactor. For example, if 2.5% by weight of hydrolyzable silane and 0.25% by weight of polymerization initiator are fed into the reactor, then no CTA is employed and the peroxide is not in a mixture

24 / 54 with a solvent, then 97.25% by weight (ie 100 to 2.5 to 0.25) ethylene component is introduced into the reactor.

[0063] The components added to the reactor can be copolymerized at temperatures from 180°C to 400°C and pressures from 5,000 psi (34.5 MPa) to 50,000 psi (344.7 MPa). According to the modalities, the components added to the reactor can be copolymerized at temperatures from 190 °C to 400 °C, such as from 200 °C to 400 °C, from 210 °C to 400 °C, from 220 °C to 400 °C, from 230 °C to 400 ºC, from 240 ºC to 400 ºC, from 245 ºC to 400 ºC, from 250 ºC to 255 ºC, from 260 ºC to 400 ºC, from 265 ºC to 400 ºC, from 270 ºC to 400 ºC, from 275 ºC to 400 ºC , from 280 °C to 400 °C, from 285 °C to 400 °C, from 290 °C to 400 °C, from 295 °C to 400 °C, from 300 °C to 400 °C, from 305 °C to 400 °C, from 310 °C to 400 °C, from 315 ºC to 400 ºC, from 320 ºC to 400 ºC, from 325 ºC to 400 ºC, from 330 ºC to 400 ºC, from 340 ºC to 400 ºC, from 350 ºC to 400 ºC, from 360 ºC to 400 ºC, from 370 ºC to 400 ºC, from 380 ºC to 400 ºC, or from 390 ºC to 400 ºC. In some modalities, the components added to the reactor can be copolymerized at temperatures from 190 ºC to 390 ºC, such as from 190 ºC to 380 ºC, from 190 ºC to 370 ºC, from 190 ºC to 360 ºC, from 190 ºC to 350 ºC, from 190 ºC to 340 ºC, from 190 ºC to 330 ºC, from 190 ºC to 325 ºC, from 190 ºC to 320 ºC, from 190 ºC to 315 ºC, from 190 ºC to 310 ºC, from 190 ºC to 305 ºC, from 190 ºC to 300 ºC, from 190 ºC to 295 ºC, from 190 ºC to 290 ºC, from 190 ºC to 285 ºC, from 190 ºC to 280 ºC, from 190 ºC to 275 ºC, from 190 ºC to 270 ºC, from 190 ºC to 265 ºC, from 190 ºC to 260 ºC, from 190 ºC to 255 ºC, from 190 ºC to 250 ºC, from 190 ºC to 245 ºC, from 190 ºC to 240 ºC, from 190 ºC to 230 ºC, from 190 ºC to 220 ºC, from 190 ºC to 210 ºC, or from 190 ºC to 200 ºC. According to other modalities, the components added to the reactor can be copolymerized at temperatures from 190 °C to 330 °C, such as from 200 °C to 325 °C, from 210 °C to 320 °C, from 220 °C to 315 °C, from 230 °C to 310 ºC, from 240 ºC to 305 ºC, from 245 ºC to 300 ºC, or from 250 ºC to 295 ºC.

[0064] The components added to the reactor may, according to

25 / 54 the modalities, be copolymerized at pressures of 10,000 psi (69.0 MPa) to

45,000 psi (310.3 MPa), such as from 13,000 psi (89.6 MPa) to 40,000 psi (275.8 MPa), from 16,000 psi (110.3 MPa) to 35,000 psi (241.3 MPa), to 18,000 psi (124.1 MPa) to 35,000 psi (241.3 MPa), from 20,000 psi (137.9 MPa) to 35,000 psi (241.3 MPa), from 22,000 psi (151.7 MPa) to 35,000 psi (241 .3 MPa), of

24,000 psi (165.5 MPa) to 35,000 psi (241.3 MPa), from 26,000 psi (179.3 MPa) to 35,000 psi (241.3 MPa), from 28,000 psi (193.1 MPa) to 35,000 psi ( 241.3 MPa), from 30,000 psi (206.8 MPa) to 35,000 psi (241.3 MPa), from 32,000 psi (220.6 MPa) to 35,000 psi (241.3 MPa), or from 34,000 psi (234 .4 MPa) to

35,000 psi (241.3 MPa). According to some modalities, the components added to the reactor can be copolymerized at pressures of

15,000 psi (103.4 MPa) to 34,000 psi (234.4 MPa), such as from 15,000 psi (103.4 MPa) to 32,000 psi (220.6 MPa), from 15,000 psi (103.4 MPa) to 30,000 psi (206.8 MPa), from 15,000 psi (103.4 MPa) to 28,000 psi (193.1 MPa), from

15,000 psi (103.4 MPa) to 26,000 psi (179.3 MPa), from 15,000 psi (103.4 MPa) to 24,000 psi (165.5 MPa), from 15,000 psi (103.4 MPa) to 22,000 psi ( 151.7 MPa), from 15,000 psi (103.4 MPa) to 20,000 psi (137.91 MPa), from 15,000 psi (103.4 MPa) to 18,000 psi (124.1 MPa), or from 15,000 psi (103 .4 MPa) to

16,000 psi (110.3 MPa).

[0065] According to the modalities, the reaction can last from 10 seconds to 10 minutes, such as from 30 seconds to 10 minutes, from 1 minute to 10 minutes, from 2 minutes to 10 minutes, from 3 minutes to 10 minutes , 4 minutes to 10 minutes, 5 minutes to 10 minutes, 6 minutes to 10 minutes, 7 minutes to 10 minutes, 8 minutes to 10 minutes, or 9 minutes to 10 minutes. In the modalities, the reaction can last from 2 minutes to 9 minutes, as from 2 minutes to 8 minutes, from 2 minutes to 7 minutes, from 2 minutes to 6 minutes, from 2 minutes to 5 minutes, from 2 minutes to 4 minutes, or from 2 minutes to 3 minutes. In some modalities, the reaction can last from 3 minutes to 9 minutes, such as 4 minutes to 8

26 / 54 minutes, 5 minutes to 7 minutes or 5.5 minutes to 6.5 minutes.

[0066] In modalities, reactor production rates can range from 10 kilotonnes per year to 1,000 kilotonnes per year.

[0067] As disclosed above, the formation of a hydrolyzable ethylene silane copolymer according to the methods disclosed and described above provides a hydrolyzable ethylene silane copolymer with properties such as, for example, the ratio of "Mz(abs) )/Mw(abs)” to the polydispersion disclosed above, which is not achieved by other methods. For example, a commercially available copolymer of ethylene and hydrolyzable silane made using a conventional tubular reactor does not have the "Mz(abs)/Mw(abs)" or polydispersity or "Mz(abs)/Mw(abs)" ratio for polydispersity or “Density x Polydispersity” or “Amorphous Content at Ambient Temperature x Polydispersity” disclosed above. Furthermore, using different process parameters in an autoclave reactor, such as temperatures below 245°C with propylene as the chain transfer agent and at a pressure of 20,000 psi (137.9 MPa), will not produce an ethylene copolymer. and hydrolyzable silane with the Mz(abs)/Mw(abs) "or polydispersity or ratio of" Mz(abs)/Mw(abs)" for polydispersity or "Density x Polydispersity" or "Amorphous Content at Room Temperature x Polydispersity "disclosed in this document. Using other different process parameters in an autoclave reactor, such as a temperature of 250 °C with propylene as the chain transfer agent and at a pressure of 28,000 psi (193.1 MPa), will not produce a hydrolyzable ethylene silane copolymer having the "Mz(abs)/Mw(abs)" or polydispersity or ratio of "Mz(abs)/Mw(abs)" to polydispersity or "Density x Polydispersity" or "Amorphous content at room temperature x polydispersity" disclosed herein document. In addition, the "Mz(abs)/Mw(abs)" or polydispersity or "Mz(abs)/Mw(abs)" ratio for polydispersity or "Density x Polydispersity" or "Amorphous content to

27 / 54 room temperature x polydispersity" of the hydrolyzable ethylene silane copolymer disclosed and described herein is not an arbitrary property of the hydrolyzable ethylene silane copolymer. Rather, as disclosed above, make a crosslinkable polymeric composition by humidification with a copolymer of ethylene and hydrolyzable silane produced in accordance with the modalities disclosed and described herein, so that the copolymer of ethylene and hydrolyzable silane has the Mz( abs)/Mw(abs) and/or polydispersity and/or “Mz(abs)/Mw(abs)” ratio for polydispersity and/or “Density x Polydispersity” and/or “Amorphous content at room temperature x polydispersity” disclosed above, results in a wetting crosslinkable polymer composition with improved properties such as, for example, faster crosslinking (as determined by the number of days at fixed curing conditions taken to achieve a certain hot creep value with a catalyst for condensation of specified silanol and in a given thickness of the article manufactured from the composition). Such moisture curable polymeric compositions are described herein below.

POLYMER COMPOSITION RETICULABLE BY HUMIDIFICATION

[0068] According to the embodiments, a polymer composition crosslinkable by humidification comprises the copolymer of ethylene and hydrolyzable silane described above and a silanol condensation catalyst. In embodiments, silanol condensation catalyst is added to promote cross-linking and ensure wetting curing of the composition. Silanol condensation catalysts include (but are not limited to) Lewis and Brønsted acids and bases. Silanol condensation catalysts that can be used in the modalities are not particularly limited and may include, for example, organic bases, carboxylic acids, sulfonic acids and organometallic compounds, including organic titanates and

28 / 54 complexes or carboxylates of lead, cobalt, iron, nickel, zinc and tin, such as dibutyltindilaurate, dioctyltindilaurate, dibutyltindiacetate, dibutyltindioctoate, stannous acetate, stannous octoate, lead naphthenate, zinc caprylate, cobalt naphthenate; It's similar. In some embodiments, the silanol condensation catalyst can be a hydrophobic catalyst, such as a hydrophobic acid catalyst. Examples of hydrophobic acid catalysts are the hydrophobic sulfonic acid catalysts that are available from King Industries, such as (but not limited to) Nacure® CD-2120 and Nacure® CD-2180. In one embodiment, the silanol condensation catalyst is included in a catalyst masterbatch mixture and the catalyst masterbatch mixture is included in the composition. In one embodiment, the silanol condensation catalyst is a mixture of catalyst masterbatch or silanol condensation catalyst masterbatch.

[0069] In embodiments, the silanol condensation catalyst can be added as a masterbatch. The use of master batches to more effectively incorporate ingredients, including those used at low levels, into polyolefin resins is well known. This procedure is also useful as it minimizes the number of materials that must be stored and handled by processors.

[0070] Master batches according to the modalities are prepared in the same manner as any polyolefin composition, such as by dry blending and/or melt blending the ingredients into a relatively homogeneous mass. The masterbatch, typically in pellet form or some other form suitable for storage and/or handling, is then "downloaded" into (i.e., blended with) hydrolyzable ethylene silane copolymer to which other ingredients or additives may already have been added, in an amount calculated to achieve the desired level of “discharge” additives in the final product. These other additives can be added directly or

29 / 54 may also be added as part of a masterbatch, as added as part of the silanol condensation catalyst masterbatch, or as part of the masterbatch comprising flame retardants, or as part of another different masterbatch, or as part of a masterbatch that contains a combination of two or more types of additives, such as silanol condensation catalyst, flame retardants, flame retardants, antioxidants, stabilizers, pigments, etc. If a masterbatch contains silanol condensation catalyst, as well as one or more additives such as (but not limited to) flame retardants and pigments, it is also called a silanol condensation catalyst or catalyst masterbatch mixture or masterbatch of silanol condensation catalyst.

[0071] According to the modalities, the silanol condensation catalyst or catalyst masterbatch mixture or silanol condensation catalyst masterbatch will be present in a polymeric composition crosslinkable by humidification in an amount of 0.0% by weight to 90.0% by weight, such as from 0.0% by weight to 80.0% by weight, from 0.0% by weight to 70.0% by weight, from 0.0% by weight to 60% by weight, from 0.0% by weight to 50% by weight, from 0.0% by weight to 40% by weight, from 0.0% by weight to 30% by weight, from 0.0% by weight to 20 0.0% by weight, from 0.01% by weight to 20.0% by weight, from 0.03% by weight to 20.0% by weight, from 0.05% by weight to 20.0% by weight from 0.10% by weight to 20.0% by weight, from 0.15% by weight to 20.0% by weight, from 0.20% by weight to 20.0% by weight, from 0.25 % by weight to 20.0% by weight, from 0.30% by weight to 20.0% by weight, from 0.35% by weight to 20.0% by weight, from 0.40% by weight to 20 0.0% by weight, from 0.45% by weight to 20.0% by weight, from 0.50% by weight to 20.0% by weight, from 0.60% by weight to 20.0% by weight , from 0.70% by weight to 20.0% by weight alone or from 0.80% by weight to 20.0% by weight. In some embodiments, the silanol condensation catalyst or catalyst masterbatch mixture or silanol condensation catalyst masterbatch

silanol will be present in a polymeric composition crosslinkable by humidification in an amount of 0.0% by weight to 89.0% by weight, as 0.0 to 79.0% by weight, from 0.0% by weight to 69.0% by weight, from 0.0% by weight to 59.0% by weight, from 0.0% by weight to 49.0% by weight, from 0.0% by weight to 39. 0% by weight, from 0.0% by weight to 29.0% by weight, from 0.0% by weight to 19.0% by weight%, from 0.0% by weight to 18.0% by weight from 0.0% by weight to 17.0% by weight, from 0.0% by weight to 16.0% by weight, from 0.0% by weight to 15.0% by weight, from 0.0 % by weight to 14.0% by weight, from 0.0% by weight % to 13.0% by weight, from 0.0% by weight to 12.0% by weight, from 0.0% by weight to 11.0% by weight, from 0.0% by weight to 10.0% by weight, from 0.0% by weight to 9.0% by weight, from 0.0% by weight to 8.0% by weight from 0.0% by weight to 7.0% by weight, from 0.0% by weight to 6.0% by weight, from 0.0% by weight to 5.0% by weight, from 0. 0% by weight to 4.0% by weight, from 0.0% by weight to 3.0% by weight, from 0.0% by weight to 2.0% by weight, or from 0.0% by weight to 1.0% by weight. In embodiments, the silanol condensation catalyst or catalyst masterbatch mixture or silanol condensation catalyst masterbatch will be present in a polymeric composition crosslinkable by wetting in an amount of from 0.01% by weight to 89.0% by weight, such as from 0.01% by weight to 79.0% by weight, from 0.01% by weight to 69.0% by weight, from 0.01% by weight to 59.0% by weight, of 0 0.01% by weight to 49.0% by weight, from 0.01% by weight to 39.0% by weight, from 0.01% by weight to 29.0% by weight, from 0.01% by weight to 19.0% by weight, from 0.03% by weight to 18.0% by weight, from 0.05% by weight to 17.0% by weight, from 0.10% by weight to 16.0% by weight, from 0.15% by weight to 15.0% by weight, from 0.20% by weight to 14.0% by weight, from 0.25% by weight to 13.0% by weight or about 8% by weight.

[0072] In embodiments, the remainder of the polymer composition crosslinkable by humidification comprises a copolymer of ethylene and hydrolyzable silane. Thus, the humidification crosslinkable polymer composition comprises a copolymer of ethylene and silane hydrolyzable in amounts of

31/54

10.0% by weight to 100.0% by weight, such as from 20.0% by weight to 100.0% by weight, from 30.0% by weight to 100.0% by weight, from 40.0% by weight % to 100% by weight, from 50.0% by weight to 100% by weight, from 60.0% by weight to 100% by weight, from 70.0% by weight to 100% by weight, from 80 0.0% by weight to 100.0% by weight, from 82.0% by weight to 100.0% by weight, from 84.0% by weight to 100.0% by weight, from 86.0% by weight to 100.0% by weight, from 88.0% by weight to 100.0% by weight, from 90.0% by weight to 100.0% by weight, from 92.0% by weight to 100.0% by weight, from 94.0% by weight to 100.0% by weight, from 96.0% by weight to 100.0% by weight or from 98.0% by weight to 100.0% by weight.

In embodiments, the humidification crosslinkable polymeric composition comprises a copolymer of ethylene and hydrolyzable silane in amounts from 11.0% by weight to 100.0% by weight, such as from 21.0 to 100.0% by weight, of 31. 0% by weight to 100.0% by weight, from 41.0% by weight to 100.0% by weight, from 51.0% by weight to 100.0% by weight, from 61.0% by weight to 100.0% by weight, from 71.0% by weight to 100.0% by weight, from 81.0% by weight to 100.0% by weight, from 82.0% by weight to 100.0% by from 83.0% by weight to 100.0% by weight, from 84.0% by weight to 100.0% by weight, from 85.0% by weight to 100.0% by weight, of 86. 0% by weight to 100.0% by weight, from 87.0% by weight to 100.0% by weight, from 88.0% by weight to 100.0% by weight, from 89.0% by weight to 100.0% by weight, from 90.0% by weight to 100.0% by weight, from 91.0% by weight to 100.0% by weight, from 92.0% by weight to 100.0% by from 93.0% by weight to 100.0% by weight, from 94.0% by weight to 100.0% by weight, or from 95.0% by weight to 100.0% by weight, of 96 0.0% by weight to 100.0% by weight, from 97.0% by weight to 100.0% by weight, from 98.0% by weight to 100.0% by weight, from 99.0% by weight to 100.0% by weight, from 80.0% by weight to 98.0% by weight, from 80.0% by weight to 96.0% by weight, from 80.0% by weight to 94.0% by weight, from 80.0% by weight to 92.0% by weight, from 80.0% by weight to 90.0% wt%, from 80, 0% by weight to 88.0% by weight, from 80.0% by weight to 86.0% by weight, from 80.0% by weight to 84.0% by weight or from 80.0% by weight to 82.0% by weight.

In some embodiments, the polymer composition crosslinkable by

Humidification comprises a hydrolyzable copolymer of ethylene and silane in amounts from 11.0% by weight to 99.99% by weight, such as from 21.0% by weight to 99.99% by weight, from 31.0% by weight to 99.99% by weight, from 41.0% by weight to 99.99% by weight, from 51.0% by weight to 99.99% by weight, from 61.0% by weight to 99. 99% by weight, from 71.9% by weight to 99.99% by weight, from 81.9% by weight to 99.99% by weight, from 82.0% by weight to 99.97% by weight, from 83.0% by weight to 99.95% by weight, from 84.0% by weight to 99.90% by weight, from 85.0% by weight to 99.85% by weight, from 86.0% by weight to 99.80% by weight, from 87.0% by weight to 99.75% by weight, from 88.5% by weight to 95.5% by weight, such as from 89.0% by weight to 95% 0.0% by weight, from 89.5% by weight to 94.5% by weight, from 90.0% by weight to 94.0% by weight, from 90.5% by weight to 93.5% by weight , or from 91.0% by weight to 92.0% by weight or about 92% by weight.

[0073] The composition of the crosslinkable polymeric composition by humidification can be carried out by standard methods. Examples of compounding equipment include internal batch mixers such as a BANBURYTM or BOLLINGTM internal mixer. Alternatively, continuous single or twin screw mixers can be used, such as a ribbon extrusion configuration, FARRELTM continuous mixer, a WERNER AND PFLEIDERERERTM twin screw mixer or a BUSSTM continuous kneading extruder. The type of mixer used and the operating conditions of the mixer will affect the properties of the composition and the manufactured article, such as viscosity, bulk resistivity and extruded surface smoothness, and these are well known to those skilled in the art.

[0074] As disclosed above, one of the unexpected properties obtained using a copolymer of ethylene and hydrolyzable silane that has the properties disclosed herein and/or produced according to the methods disclosed herein is faster crosslinking (as determined by the number of days in curing conditions

33 / 54 fixtures taken to achieve a certain hot creep value with a specified silanol condensation catalyst or catalyst masterbatch mixture or silanol condensation catalyst masterbatch and at a given thickness of the article manufactured from the composition). In one embodiment, the polymeric composition crosslinkable by humidification has a hot creep, measured at 0.2 MPa and 150 °C or 200 °C in extruded tape having a thickness of 50 mil (1.270 mm) to 80 mil (2.032 mm), or 60 thousand (1.524 mm) to 70 thousand (1.778 mm), less than or equal to 100% within 15 days or less than or equal to 80% within 23 days, in which the tape produced from the polymeric composition crosslinkable by humidification was cured at 23°C and 50% relative humidity.

[0075] In some embodiments, the polymer composition crosslinkable by humidification has a hot creep - measured as disclosed above - less than or equal to 95% in 15 days, less than or equal to 90% in 15 days, less than or equal to 85 % in 15 days, less than or equal to 80% in 15 days, or less than or equal to 75% in 15 days. In some embodiments, the polymeric composition crosslinkable by humidification has a hot creep - measured as disclosed above - less than or equal to 75% in 23 days, less than or equal to 70% in 23 days, less than or equal to 65% in 23 days days, less than or equal to 60% in 23 days, or less than or equal to 55% in 23 days.

[0076] According to some embodiments, the polymer composition crosslinkable by humidification has a hot creep, measured at 0.2 MPa and 150 °C or 200 °C in extruded tape with a thickness of 30 mil (0.762 mm) to 80 mil ( 2.032 mm), of less than or equal to 175% after curing the tape for 4 hours to 20 hours in a water bath at 90 °C, as less than or equal to 150% after curing the tape for 4 hours to 20 hours in a bath - water at 90 °C, less than or equal to 125% after curing the tape for 4 hours to 20 hours in a bain-marie at 90 °C, less than or equal to 100% after curing the tape for 4 hours to 20 hours in a bath -mary at 90°C, less than or equal to 80% after the tape has been cured for 4

34 / 54 hours to 20 hours in a water bath at 90 °C, or less than or equal to 60% after curing the tape for 4 hours to 20 hours in a water bath at 90 °C, or less than or equal to 50% after curing of the tape for 4 hours to 20 hours in a water bath at 90 °C, or less than or equal to 40% after curing the tape for 4 hours to 20 hours in a water bath at 90 °C, or less than or equal to 30% after tape cure for 4 hours to 20 hours in a water bath at 90 °C, or less than or equal to 25% after curing the tape for 4 hours to 20 hours in a water bath at 90 °C, or less than or equal to 20% after curing the tape for 4 hours to 20 hours in a water bath at 90 °C, or less than or equal to 15% after curing the tape for 4 hours to 20 hours in a water bath at 90 °C, or less than or equal to 10 % after curing the tape for 4 hours to 20 hours in a water bath at 90 °C, or less than or equal to 5% after curing the tape for 4 hours to 20 hours in a water bath at 90 °C.

[0077] In addition to ethylene hydrolyzable silane copolymer and silanol condensation catalyst or catalyst masterbatch or silanol condensation catalyst masterbatch, the humidification crosslinkable polymer composition may comprise various additives conventionally added to humidification crosslinkable polymer compositions . Such additives include (but are not limited to) antioxidants, burn retardants (including, but not limited to, wetting removers), flame retardants (including organic fillers), UV stabilizers and absorbers (including carbon black), metal deactivators ( such as, for example, oxalyl bis(benzylidene)hydrazide), non-silane functional polyolefins, silicones and mixtures thereof.

[0078] According to one or more embodiments, the humidification cure polymeric composition may comprise: (A) the copolymer of ethylene and hydrolyzable silane disclosed and described herein in amounts from 10.00 to less than 100.00% by weight, such as from 10.00 to 99.95% by weight, from 20.00% by weight to less than 100.00% by weight, from 30.00% by weight to 99.00% by weight, from 40 .00% by weight to 97.00% by weight, or from 50.00%

35 / 54 by weight to 96% by weight, or from 60.00 to 98.00% by weight, or from 70.00 to 99.00% by weight, or from 80.00 to 99.50% by weight, or from 90.00 to 99.90% by weight; (B) the silanol condensation catalyst or catalyst masterbatch mixture or silanol condensation catalyst masterbatch disclosed and described herein in amounts of 0.00% by weight, or 0.05% by weight to 90.0% by weight, from more than 0.00% by weight to 20.00% by weight, from 0.05% by weight to 15.00% by weight, from 0.10% by weight to 10.00 % by weight or from 0.15% by weight to 5.00% by weight; (C) wetting removers or burn retardants from 0.00% by weight to 5.00% by weight, such as from 0.10% by weight to 3.00% by weight, 0.20% by weight to 2. 00% by weight, from 0.30% by weight to 1.00% by weight; (D) antioxidants in amounts from 0.00% by weight to 2.00% by weight, from 0.01% by weight to 1.50% by weight, from 0.02% by weight to 1.00% by weight or from 0.03% by weight to 0.70% by weight; and (E) flame retardants in amounts from 0.00% by weight to 90.00% by weight, such as from 0.00% by weight to 80.00% by weight, from 10.00% by weight to 70, 00% by weight, from 20.00% by weight to 60.00% by weight, or from 30.00% by weight% to 50.00% by weight.

It should be understood that, according to the modalities, additional additives - such as UV stabilizers and absorbers, metal deactivators, polyolefins without silane functionality and silicones - can be added to the crosslinkable polymer composition by humidification in smaller or larger amounts (individually or in aggregate), such as less than 90.00% by weight, less than 80.00% by weight, less than 70.00% by weight, less than 60.00% by weight, less than 50.00% by weight, less than 40.00% by weight, less than 30.00% by weight, less than 20.00% by weight, less than 10.00% by weight, less than 8.00% by weight, less than 6.00 % by weight, less than 4.00% by weight, less than 2.00% by weight, less than 1.00% by weight, less than 0.50% by weight, less than 0.25% by weight, less of 0.20% by weight or less than 0.10% by weight.

It should also be understood that, according to modalities, any of the above ranges

36 / 54 can be combined with any of the above ranges.

PRODUCTS COMPOSED BY POLYMER COMPOSITION HUMIDIFICATION CROSS-BLOCK

[0079] The wetting crosslinkable polymer composition can be applied to a conductor as a coating (including a sheath that is an insulation and/or a protective jacket) in known quantities or thicknesses and by known methods to make an article that is a wire or cable (for example, with the equipment and methods described in US Patent Nos. 5,246,783 and 4,144,202, each of which are incorporated herein by reference in their entirety). Typically, the polymer composition is prepared in an extruder equipped with a conductor coating die, and after the composition is formulated, the composition is extruded onto the conductor as the conductor is pulled through the die.

[0080] Other articles of manufacture that can be prepared from the crosslinkable polymeric composition by humidification, particularly under high pressure and/or high temperature and/or high humidification conditions, include fibers, strips, sheets, tapes, tubes, pipes, sealing, gaskets, foams, shoes and bellows. These items can be manufactured using known equipment and techniques.

[0081] Articles produced from the polymeric compositions curable by humidification can be cured by moisture in a water bath or a sauna or under environmental conditions to affect crosslinking. The time to complete crosslinking will depend on conditions such as article or coating thickness, temperature, humidity, catalyst used, etc.

EXAMPLES

[0082] Modalities will be better explained by the following examples.

TEST CONDITIONS AND PARAMETERS DENSITY

37 / 54

[0083] Ethylene-based polymers that are density tested are prepared in accordance with ASTM D 1928. The samples are pressed at 374°F (190°C) and 30,000 psi (207 MPa) for three minutes and then , at 70°F (21°C) and 30,000 psi (207 MPa) for one minute. Density measurements are taken after 40 hours of sample pressing, using ASTM D792, Method B.

UNSATURATION CONTENT

[0084] The unsaturation content of ethylene-based polymers (including terminal vinyls per 1,000 carbon atoms) is determined by nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (for example, according to the described procedure in US patent number 8,912,297 B2) or any other known method (or method yet to be developed). An example of an NMR spectroscopic method used to determine types and amounts of unsaturation in ethylene-based polymers can be found in Busico, V., et al., Macromolecules, 2005, 38, 6988. Proton (1H) NMR is used for this purpose in this study.

LONG CHAIN BRANCHING CONTENT

[0085] The content of long chain branching (LCB; C6 and higher per

1,000 carbon atoms) is determined by 13C NMR.

CRYSTALINITY

[0086] Crystallinity of any ethylenic polymer is measured as follows: Determine melting peaks and percentage (%) or percentage by weight (% by weight) of ethylene polymer crystallinity using a Differential Scanning Calorimetry instrument ( DSC) DSC Q1000 (TA Instruments).

[0087] (A) Baseline calibration instrument. Use software calibration wizard. First, obtain a baseline by heating a cell from -80° to 280°C without any sample in a

38 / 54 aluminum DSC pan. Then use sapphire standards as instructed by the calibration wizard. Analysis of 1 to 2 milligrams (mg) of a new indium sample by heating the standard sample to 180 °C, cooling to 120 °C at a cooling rate of 10 °C/minute, then maintaining the standards isothermally at 120°C for 1 minute, followed by heating the standard sample from 120°C to 180°C at a heating rate of 10°C/minute. Determine which sample of indium standards has heat of fusion = 28.71 ± 0.50 Joules per gram (J/g) and start of fusion = 156.6 °C ± 0.5 °C.

[0088] (B) Perform DSC measurements on test samples using the same DSC instrument. Press the semi-crystalline ethylenic polymer test sample into a thin film at a temperature of 160°C. Weigh 5 to 8 mg of test sample film into DSC pan. Crimp the lid onto the pan to seal the pan and ensure a closed atmosphere. Place the sealed pan in the DSC cell, balance the cell at 30°C and heat at a rate of about 100°C/minute to 190°C, keep the sample at 190°C for 3 minutes, cool the sample at a rate of 10°C /minute at -60 °C to obtain a heat of fusion (Hf) cooling curve, and hold isothermally at -60 °C for 3 minutes. Then heat the sample again at a rate of 10 °C/minute to 190 °C to obtain a second heat of fusion heating curve (ΔHf). Using the second heating curve, calculate the “total” heat of fusion (J/g) by integrating from –20 °C (in the case of ethylene homopolymers, hydrolyzable ethylene copolymers and silane monomers, and alpha olefinic ethylene copolymers of density greater than, equal to or greater than 0.90 g/cm3) or −40 ºC (in the case of copolymers of ethylene and unsaturated esters, and ethylene alpha olefin copolymers with a density less than 0.90 g/cm3) at the end of Fusion. Using the second heating curve, calculate the heat of fusion at “ambient temperature” (J/g) of 23°C (room temperature) until the end of fusion, dropping perpendicularly to 23°C. Measure and report the "total crystallinity" (calculated at

39 / 54 from the “total” heat of fusion) as well as “room temperature crystallinity” (calculated from the “room temperature” heat of fusion). Crystallinity is measured and reported as percent crystallinity (%) or percent by weight (% by weight) of the polymer from the test sample's second heat of fusion heat curve (ΔHf) and its normalization to the heat of fusion of 100% crystalline polyethylene, where % crystallinity or crystallinity in % by weight = (ΔHf*100%)/292 J/g, where ΔHf is as defined above, * indicates mathematical multiplication, / indicates mathematical division and 292 J /g is a literature value of heat of fusion (ΔHf) for a 100% crystalline polyethylene.

HOT FLUENCE

[0089] Hot creep (also known as hot set elongation, HSE) is measured to determine the degree of cure (crosslinking). The tests are based on the Insulated Cable Engineers Association's ICEA-T-28-562-2003 standard for power cable insulation materials. The specimens are taken along the extrusion direction of crosslinked tapes with thickness values ranging from 30 mil (0.762 mm) to 80 mil (2.032 mm). Three test specimens from each sample are cut using ASTM D 412 Type D drawbars (dumbbells). The hot creep test is conducted on samples (of measured thickness values) in an oven with a glass door set at 150 °C or 200 °C with a force of 0.2 MPa of tension applied to the underside of the specimens. Test specimens are fixed vertically from the upper ends in the oven with load attached to the lower end of each test specimen. The specimens are subjected to the hot creep test for 15 minutes at a fixed temperature and the percentage increases in length are measured over this time, with the mean values of the three measurements reported as “hot creep”. Hot creep percentage (or HSE) values are calculated as stipulated in [0123] of document number

40 / 54 EP2508566, which is incorporated herein by reference in its entirety.

FUSION INDEX

[0090] The melt index (I2) values of ethylene-based polymers are measured according to ASTM D1238 at 190°C at 2.16 kg.

GEL PERMEATION CHROMATOGRAPHY

[0091] A Triple Detector Gel Permeation Chromatography system (3D-GPC or TDGPC) consisting of a PolymerChar (Valencia, Spain) GPC-IR high temperature chromatograph, equipped with a laser light scattering detector of 2 angles (LS) Model 2040 from Precision Detectors, now Agilent Technologies (CA, USA) and a PolymerChar 4-capillary solution (DP) viscometer is used. Data collection is performed using Polymer Char “GPC One” software. The system is also equipped with an in-line solvent degassing device from Agilent Technologies.

[0092] High Temperature GPC Columns consisting of four 30 cm, 20 µm mixed A LS columns from Agilent Technologies are used. The GPC-IR automatic autosampler oven is operated at 160 °C and the column compartment is operated at 150 °C. Samples are prepared semi-automatically by dosing the GPC-IR syringe at a concentration of 2 mg/ml with a decani flow rate marker supplied by means of a micropump. The chromatographic solvent and sample preparation solvent is 1,2,4-dichlorobenzene (TAB) which contains 200 ppm of 2,6-di-tart-butyl-4methylphenol (BHT). The solvent is sparged with nitrogen. Polymer samples are stirred at 160°C for three hours. The injection volume is 200 microliters. The flow rate through the GPC is fixed at 1.0 ml/minute.

[0093] Column calibration and sample molecular weight calculation are performed using Polymer Char “GPC One” software. THE

41 / 54 Calibration of the GPC columns is performed with 21 narrow molecular weight distribution polystyrene standards obtained from Polymer Laboratories (now Agilent Technologies). The molecular weights of the polystyrene standards range from 580 to 8,400,000 g/mol and are arranged in 6 “cocktail” mixtures with at least a decade of separation between the individual molecular weights with individual concentrations ranging from 0.25 (Mp> 500,000) at 0.5 mg/ml (Mp<500,000) by dissolving for 24 hours in TCB at room temperature in a dark environment.

The maximum molecular weights of polystyrene standards are converted to polyethylene molecular weights using the following equation (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)): Polyethylene=A(Polystyrene)B

[0095] Here, B has a value of 1.0, and the experimentally determined value of A is around 0.38 to 0.44.

[0096] The column calibration curve is obtained by fitting a first-order polynomial to the respective polyethylene equivalent calibration points, obtained from the Equation above, to the observed elution volumes.

[0097] The conventional number and the weight average molecular weights (Mn(conv) and Mw(conv), respectively) are calculated according to the following equations: where Wfi is the fraction by weight of the i-th component and Mi is the molecular weight of the ith component. Polydispersity or molecular weight distribution (MWD) is expressed as the ratio of the conventional weight average molecular weight (Mw) to the conventional number average molecular weight (Mn), i.e., Mw (conv)/Mn (conv).

42 / 54

[0098] The value of A above is determined by fitting the value A in the Williams and Ward Equation to Mw, the weighted average molecular weight, calculated using the above equation, and the corresponding retention volume polynomial agreed with the value independently determined from Mw, obtained in accordance with the linear reference homopolymer with known weight average molecular weight of 115,000 g/mol as measured by LALLS in a traceable manner to standard polyethylene homopolymer NBS1475.

[0099] The absolute weight average molecular weight (Mw(abs)) is characterized by the LS (15 degree angle) and IR-5 (measurement signal) concentration detectors subtracted from the baseline using the following equation: where is the response area of the LS detector, is the response area of the IR-4 detector, and is the instrument constant that was determined using a NIST 1475 standard with known concentration and certified value for a weight average molecular weight of 52,000 g/mol.

[00100] The absolute molecular weight in each elution volume is calculated using the following equation: where is the instrument constant determined, and is the LS (15 degrees) and IR5 (measurement) detector responses subtracted from the baseline of the same i-th elution component.

[00101] The average absolute number and the average molecular weight z are calculated with the following equations:

[00102] A linear extrapolation was performed on the volume graph of

43 / 54 MLS log elution, i when MLS log data, i scattered caused by low LS or IR detector responses.

[00103] The ratio between the mean absolute molecular weight z and the mean absolute molecular weight (Mz(abs)/Mw(abs)) is calculated.

FTIR TEST METHOD FOR CHARACTERIZATION OF VTMS CONTENT IN COPOLYMERS:

[00104] FTIR was used to determine the % by weight of VTMS present in the copolymer samples. The method is based on measuring absorbance at 1193 cm-1 (Si-O-CH3) and 2019 cm-1 (path length normalization band) with baseline points set at 1230 cm-1 at 1,165 cm -1 and 2,106 cm-1 to 1,979 cm-1, respectively. The peak height ratio of 1,193/2019 is compared to standards with known VTMS levels. Sample films approximately 0.07 mm (3 mils) thick are compression molded between Teflon sheets using a hydraulic press. Films are prepared by pre-heating the sample to 190°C with partially closed heated plates (1/8” interval between the top and bottom plates) for 1 min, followed by pressing the sample for 30 s at 18,143 kg (40,000 lbs) . The sample is allowed to cool to room temperature on the laboratory bench and used for analysis. X-RAY FLUORESCENCE (XRF) TEST METHOD FOR

CHARACTERIZATION OF HYDROLYZABLE SILANO GROUP CONTENT IN COPOLYMERS:

[00105] The silicon (Si) content (% by weight) in the copolymer was also determined using X-ray fluorescence (XRF). Details of the test method employed are provided below.

[00106] The powder sample was pressed onto a board approximately 6 mm thick using a Buehler SimpliMet 300 automatic assembly press [3 min preheating; followed by

44 / 54 hold time of 1 min at 240°F (115.6°C), under 1,200 psi (8.3 MPa, 84.4 kg/cm2) pressure and cooled to room temperature]. The Si content was analyzed by wavelength dispersive XRF (PANalytical Axios).

[00107] The PANalytical Axios is a wavelength dispersive X-ray spectrometer. The basic principle of this analytical technique is as follows. A sample of the appropriate size and dimension is placed in an analysis cup and irradiated with radiation from an X-ray tube. These X-rays make the elements (F to U) of the sample go through the fluorescence process with secondary X-ray emission. Each element produces fluorescent X-rays at specific energies and wavelengths. These secondary X-rays are scattered with appropriately spaced diffraction crystals and are measured by flux or scintillation detectors set at specific angles to lines of interest.

[00108] The analyte concentration is determined by comparing the intensity of the line with an established calibration curve, for the element of interest. The calibration curve is established using polymer standards with known concentrations of the element of interest analyzed by neutron activation (NAA) or inductively coupled plasma (ICP) analysis.

[00109] The XRF results show the total content (% by weight) of Si, which is then used to calculate the content (% by weight) of hydrolyzable silane groups in the copolymer from the molecular weight of the hydrolyzable silane groups (which, in the case of VTMS, it is 148.23 g/mol).

[00110] NMR test method for characterization of total hydrolyzable silane group content in copolymers and primary hydrolyzable silane group content:

[00111] As an alternative to XRF and FTIR, proton (1H) NMR was used to measure the content of total hydrolyzable silane groups in copolymers (moles Si(OCH3)3 / 1000 C), as well as the content of hydrolyzable silane groups

45 / 54 terminals (mols Si-CH2 / 1000 C). Content of hydrolyzable silane groups (% by weight) = 100 x [(moles Si(OCH3)3 / 1000 C x "molecular weight of hydrolysable silane groups in g/mol")/(moles Si(OCH3)3 / 1000 C x “molecular weight of hydrolysable silane groups in g/mol”+1,000x14)]. In the case of VTMS, the molecular weight of the hydrolyzable silane groups is 148.23 g/mol. CALCULATION OF THE CONTENT OF HYDROLYZABLE SILANA GROUPS OF % MOL IN FTIR, XRF AND NMR MEASUREMENT COPOLYMERS:

[00112] The mol% of hydrolyzable silane groups = ("% by weight of hydrolyzable silane groups"/"molecular weight of hydrolyzable silane groups in g/mol")/(("% by weight of silane groups hydrolysables"/"molecular weight of hydrolysable silane groups in g/mol") + ((100-"% by weight of hydrolysable silane groups)/"molecular weight of ethylene in g/mol")) x 100. EXAMPLES 1 A 3 AND COMPARATIVE EXAMPLES 1 TO 3

[00113] Preparation of ethylene reactor copolymer-VTMS: The amounts of each of the materials used in these examples and comparative examples are given in Table 1 below. Generally, in a stirred autoclave with a capacity of 545 milliliters (ml), a mixture of ethylene, vinyltrimethoxysilane (VTMS; XIAMETER™ OFS-6300 Silane (product of Dow Silicones Corporation); KBM-1003 (product of Shin-Etsu Chemical Company) and optionally propylene (as a chain transfer agent used in Comparative Examples 1 to 3) was loaded. t-Butyl peroxyacetate (PA; Luperox 7M75 (manufactured by Arkema); Trigonox F-C50 (manufactured by Sigma Aldrich) ) or t-butyl peroxy-2-ethylhexanoate (PO; Luperox 26 (manufactured by Arkema); Trigonox 21S (manufactured by Sigma Aldrich)), the former with loadings of 0.25% by weight or 0.2% by weight and the latter with 2% by weight or 3% by weight of a 5% by weight solution in odorless mineral alcohol was added as a polymerization initiator to the mixture, which was subjected to a defined pressure of

46 / 54 approximately 20,000 psi (1,406 kg/cm2) or 28,000 psi (1,969 kg/cm2). Temperatures were adjusted to range from approximately 190 °C to approximately 250 °C (as shown in Table 1). Under these and other conditions, as shown in Table 1, ethylene-VTMS copolymers were continuously synthesized and subsequently converted to pellet forms by melt extrusion. The conditions listed in Table 1 are averages over the period of time the samples were collected. The "autoclaved" experimental reactor copolymers thus formed have the characteristics set forth in Table 2 and Table 3. All copolymers contained essentially similar amounts of VTMS (approximately 1.5% by weight as measured by FTIR or XRF), but there were significant differences in molecular weight characteristics and melting rheological properties. Also shown in Table 2 are the characteristics of a commercially available copolymer of ethylene and hydrolyzable silane groups (SI-LINK™ DFDA-5451 NT) produced using a conventional tubular reactor, which is also a comparative example.

[00114] In contrast to Comparative Examples 1 to 3, as well as SI-LINK™ DFDA-5451 NT, all Examples of the present disclosure desirably exhibited Mz(abs)/Mw(abs) less than or equal to 9.5, and /or the ratio of "Mz(abs)/Mw(abs)" for polydispersity less than or equal to 1.5, and/or polydispersity of 6.6 or greater, and/or "Density x polydispersity" of 6.0 or greater, and/or “Amorphous Content at Room Temperature x Polydispersity” of 360 or greater (Table 2). TABLE 1 Polymerization Conditions Temperatur Rate Rate Rate Rate Rate Conversion Supply Supply Supply Supply Supply Sample Supply Reactor, MPa Reactor, Ethylene or Propylene Initiator VTMS Ethylene (psi) (°C) kg/h ( lb/h) kg/h (lb/h) kg/h (lb/h) (cm3/h) (%) 135.0 Example 1 250.7 11.3 (25.0) 0.06 (0. 15) 0.0 33.7 (PA) 11.8 (19,582) 141.3 Example 2 250.0 11.4 (25.2) 0.07 (0.17) 0.0 32.0 (PA) 12.2 (20,503)

47 / 54 Polymerization Conditions Temperatur Rate Rate Rate Rate Rate Conversion Supply Supply Supply Supply Supply Sample Supply Reactor, MPa Reactor, Ethylene or Propylene Initiator VTMS Ethylene (psi) (°C) kg/h (lb/h) kg/h (lb/h) kg/h (lb/h) (cm3/h) (%) 134.7 Example 3 250.2 11.3 (25.0) 0.08 (0 .18) 0.0 21.2 (PA) 11.5 (19.540) Example 135.1 Comparative 220.1 11.3 (25.0) 0.09 (0.22) 0.15 (0.34) 29.6 (PO) 10.6 (19604) o1 Example 134.7 Comparative 190.1 11.3 (25.0) 0.09 (0.21) 0.34 (0.77) 29.5 (PO ) 9.2 (19,547) o2 Example 193.6 Comparative 250.1 11.3 (25.0) 0.07 (0.17) 0.19 (0.43) 31.9 (PA) 11.5 ( 28.092) o3 TABLE 2 Characteristics of the ethylene-VTMS copolymer Crystal Content LCB Content Ratio Amorphous Content Indi Mw Content Amorphous Content (C6 and Mz Amorphous o a ce of (conv) Polydi and a oa VTM superio (abs)/ à Tempe of VTM /Mn spersã Temp Temp S (% r / Density Mz(ab Mw Temper fusion fusion S (% (conv) o eratur eratur) Sample in 1000 of s)/Mw (abs) Ambie o em - xaa wt) C) (g/cm3) (abs) for Ambient x (g/1 mol) Polydi Densi Ambie Ambie - FTIR - Polydi te x Polydis 0 - spers ant FTIR (% nt (% / XRF) NMR spersi Polydisp persida min) / XRF ity in em of 13C ersity of x weight) weight)

LCB Experimental Products Example 1.47 / 0.28 / 1.61 3.103 0.9166 7.33 7.58 1.03 6.72 42.63 57.37 420.52 1304.9 1 NM NM Example 1, 57/ 0.30/ 1.07 3.276 0.9170 6.62 7.52 1.14 6.07 43.20 56.80 376.02 1231.8 2 1.64 0.31 Example 1.43/ 0 .27 / 1.83 3.107 0.9162 7.51 7.17 0.96 6.88 43.06 56.94 427.62 1328.6 3 NM NM Example 1.51/ 0.29 / Compare 1.26 2.342 0.9196 5.76 9.94 1.73 5.30 45.83 54.17 312.02 730.8

NM NM tive 1 Example 1.57/ 0.30/ Compare 2.18 2.166 0.9208 4.92 13.85 2.82 4.53 47.94 52.06 256.14 554.8 1.67 0. 32 tivo 2 Example 1.53/0.29/ Compare 1.19 2.756 0.9201 6.51 17.44 2.68 5.99 45.55 54.45 354.47 976.9 1.58 0.30 tive 3 Commercial products is SI-LINK™ 1.5 / 0.29/ 1.5 2.817 0.922 6.12 18.85 3.08 5.64 46.87 53.13 325.16 916.0 DFDA-1, 44 0.28 5451 NT NM = Not measured TABLE 3 - PROTON NMR CHARACTERIZATION

COPOLYMERS

48 / 54 silane groups c/t soft hydrolyzable trissub Content of total terminal vinyls/vinylidene content vinyls VTMS VTMS Samples the 1,000 os /1,000 - mole Si-CH2 / (% in (% in /1,000 C /1,000 CC Si(OCH3) )3/ 1,000 1,000 C weight) mol)

Ç

C Example 1 0.059 0.152 0.035 0.101 1.356 0.105 1.42 0.27 Example 2 0.060 0.168 0.038 0.079 1.266 0.079 1.32 0.25 Example 3 0.063 0.201 0.045 0.109 1.295 0.091 1.35 0.26 Comparative Example 0.066 0.130 0.150 0.019 1.342 0.081 1.40 0.27 1 Comparative Example 0.062 0.077 0.250 0.013 1.309 0.057 1.37 0.26 2 Comparative Example 0.062 0.079 0.168 0.050 1.252 0.081 1.31 0.25 3 SI-LINK™ DFDA-5451 0.046 0.037 0.232 0.133 1.290 0.057 1.35 0.26

NT EXAMPLES 4 TO 8 AND COMPARATIVE EXAMPLES 4 TO 8

[00115] The compositions of these examples and comparative examples are shown in Tables 4 to 5 below and were made as described in this document. The ethylene-VTMS copolymers of Examples 1 to 3 and Comparative Examples 1 to 3 were used as received, i.e. in the form of pellets. SI-LINK™ DFDA-5451 NT is a commercial “tubular” ethylene-VTMS copolymer (manufactured by The Dow Chemical Company), which contains 1.5% by weight of VTMS, which has a density of 0.922 g/cm3 and a melt index 1.5 g/10 min, and is also in pellet form. SI-LINK™ AC DFDB-5451 NT is a commercial “tubular” ethylene-VTMS copolymer (manufactured by The Dow Chemical Company), which contains 1.5% by weight of VTMS, which has a density of 0.922 g/cm3 and a melt index of 1.5 g/10 min, which additionally contains a burn-retardant additive (SRA) and is also in pellet form. SI-LINK™ DFDA-5451 NT and SI-LINK™ AC DFDB-5451 NT are comparative examples of commercially available copolymers of hydrolyzable ethylene and silane groups.

[00116] In the case of Example 7, a burn-retardant or humidification eliminator additive (PROSIL 9202; octyltriethoxysilane; product of

49 / 54 Milliken Chemical) was soaked in the ethylene-VTMS copolymer pellets of Example 1 as follows: PROSIL 9202 was added to the copolymer pellets in a bottle at room temperature, and tumbled for 10 minutes; the flask was placed in an oven at 70 ºC for 30 minutes, removed and turned over for 10 minutes; and the bottle containing copolymer pellets soaked in PROSIL 9202 was kept for up to 96 hours at room temperature and spun again for 10 minutes before use. Note that no burn retarding additives were adsorbed in the ethylene-VTMS copolymer pellets of Examples 1 to 3 used for Examples 4 to 6 and Example 8, nor in the ethylene-VTMS copolymer pellets of Comparative Examples 1 to 3 and SI -LINK™ DFDA-5451 NT used for Comparative Examples 4 to 6 and Comparative Example 8.

[00117] Physical blends (in a plastic bag) were made from the copolymer pellets (in the case of Example 7, also containing scorch additive) and SI-LINK™ AC DFDB-silanol condensation catalyst masterbatch pellets 5418 BK EXP1 (manufactured by The Dow Chemical Company). These were supplied to a ¾" Brabender extruder equipped with a 25:1 dual mixing zone screw (pineapple) to produce tape (using a 2" wide die from approximately 58 to 72 mil (1.5 mm to 1.8 mm) thick. The temperature profile defined by the zones was 150 ºC, 160 ºC, 170 ºC and 170 ºC in the head/matrix. A 40/60/40 mesh screen package was employed and the screw speed was 60 rpm. Note that SI-LINK™ AC DFDB-5418 BK EXP1 contains a hydrophobic acid, which functions as the silanol condensation catalyst, as well as polyethylene, carbon black, octyltriethoxysilane (n-octyltriethoxysilane), antioxidant and stabilizer.

[00118] The tapes were aged for up to 35 days at 23 ºC and 50% relative humidity (RH), as well as for 20 hours in a bain-marie at 90 ºC. Hot creep measurements were conducted after several intervals of

50 / 54 time under two different curing conditions. The results are shown in Tables 4 and 5 below. It was found that, when cured at 23°C and 50% relative humidity, the formulations of the examples according to the modalities disclosed and described herein (Examples 4 to 7) crosslink substantially faster than the comparative examples, so that the times to reach 80% hot creep were approximately 3 or 10 times shorter compared to Comparative Examples 4 and 5, respectively. Likewise, another formulation of an example in accordance with the modalities disclosed and described herein (Example 8) crosslinked substantially faster than the comparative examples, so that the time to reach 80% hot creep was approximately 3 times smaller relative to Comparative Example 8. Furthermore, the formulations of the Examples (Examples 4 to 7) exhibited crosslinking with substantially faster wetting than formulations made with commercially available comparative ethylene-VTMS copolymers (used in Comparative Examples 6 and 7). Also unexpected was the finding that the use of burn resistant additive (SRA) or humidification eliminator had much less adverse effect (if any) on the cure times of ethylene-VTMS copolymers according to the modalities (compare Example 4 with Example 7) than in the case of commercially available ethylene-VTMS comparative copolymers (Comparative Example 6 versus Comparative Example 7). In all cases, the final degrees of crosslinking obtained were similar or identical (as reflected in the hot creep values obtained after 20 hours curing in a water bath at 90°C).

[00119] Interestingly, all inventive ethylene-VTMS copolymers (of about 1.5% by weight VTMS content as measured by XRF) exhibited "Amorphous Content at Room Temperature x Polydispersity x LCB" values that were substantially bigger than the

51 / 54 comparative ethylene-VTMS copolymers (Table 2).

[00120] Regression analyzes of data (using JMP software) on all compositions except Comparative Example 7 (in which copolymer characterization data were not available in Tables 2 and 3) revealed that there were very good correlations of “Days at 100% hot creep (200°C, 0.2 MPa) at 23°C, 50% RH “or” Days at 80% hot creep (200°C, 0.2 MPa) at 23°C, 50% RH “with the following properties of ethylene-VTMS copolymers: Polydispersity, Amorphous Content at Room Temperature, Density, “Density x Polydispersity” and/or “Amorphous Content at Room Temperature x Polydispersity”. In addition, the most statistically significant variables were Polydispersity, “Density x Polydispersity” and/or “Amorphous Content at Room Temperature x Polydispersity”, as evidenced by the results of the JMP analyzes shown in Tables 6 to 7. Interestingly, density and amorphous content at room temperature were not statistically significant variables (with 95% confidence). Note that the compositions were all made with the same type and amount of silanol condensation catalyst, using ethylene-VTMS copolymers of similar VTMS grades, and that the resulting ribbons were generally of similar thickness values. TABLE 4 Example Example Example Example Example Example Example Example Compare Compare Compare Compare o4 5 6 7 active 4 active 5 active 6 active 7 Formulation (% by weight) 92.0 91.5 ethylene-VTMS copolymer pellets Example 1 Pellets of 92.0 ethylene-VTMS copolymer Example 2 92.0 ethylene-VTMS copolymer pellets Example 3 92.0 ethylene-VTMS copolymer pellets Comparative Example 1 92.0 ethylene-VTMS copolymer pellets Example Comparative 2

52 / 54 SI-LINK™ 92.0 DFDA-5451 NT Pellets SI-LINK™ AC 92.0 DFDB-5451 NT PROSILY 9202 0.5 Octyltriethoxysilane SI-LINK™ AC Pellets DFDB-5418 BK EXP1 (Master Lot 8 .0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 Silanol Condensation Catalyst)

Tape thickness (mil) 67 66 67 64 64 72 65 66 Tape thickness (mm) 1.70 1.68 1.70 1.63 1.63 1.83 1.65 1.68

Warm creep (%) - 200°C, 0.2 MPa After 3 days at 23°C, 201.18 50% RH After 4 days at 23°C, 123.11 163.74 162.57 215.49 222.22 50% RH 203.54 After 7 days at 23°C, 104.37 123.67 110.56 119.96 137.56 205.58 196.22 50% RH 127.86 After 10 days at 23°C, 89 .54 85.46 85.94 95.77 120.58 178.83 124.34 50% RH 109.87 After 14 days at 23°C, 80.50 75.97 77.91 81.13 111.13 160, 59 111.72 50% RH 96.51 After 21 days at 23°C, 69.82 65.91 70.07 69.02 92.10 143.43 98.04 50% RH 85.28 After 28 days at 23°C , 62.07 67.22 64.32 67.45 81.88 132.38 88.81 50% RH 75.03 After 35 days at 23 ºC, No No 50% RH Applicable 57.24 65.28 80.88 130.72 Not 76.29 Applicable l Applicable

TABLE 4 (CONTINUED) Example Example Example Example Example Example Example 4 5 lo 6 7 Compare Comparativ Compare Compare active 4 o5 active 6 active 7 After 20 hours at 22.20 21.05 21.77 23.29 21.54 25, 98 23.06 22.98 water bath at 90 °C

Days at 100% hot creep (200 8 9 9 10 19 ~ 80 * 13 20 °C, 0.2 MPa) at 23 °C, 50% RH Days at 80% hot creep (200 °C, 0.2 15 13 13 15 ~ 35 ~ 170 * 25 33 MPa) at 23 °C, 50% RH * predicted by curve fitting and data extrapolation

TABLE 5 Example Example 8 Comparative 8 Formulation (% by weight) Ethylene-VTMS copolymer pellets of Example 1 92.0 Ethylene-VTMS copolymer pellets of Example 92.0 Comparative 3

53 / 54 Example Example 8 Comparative 8 Formulation (% by weight) Pellets SI-LINK™ AC DFDB-5418 BK EXP1 (Batch 8.0 8.0 Silanol Condensing Catalyst Master)

Tape thickness (mil) 61 58 Tape thickness (mm) 1.55 1.47

Warm creep (%) - 200°C, 0.2 MPa After 2 days at 23°C, 50% RH 183.82 After 3 days at 23°C, 50% RH 151.90 After 4 days at 23°C, 50 % RH 129.20 196.77 After 7 days at 23°C, 50% RH 92.24 155.93 After 10 days at 23°C, 50% RH 76.56 118.14 After 14 days at 23°C, 50% RH 66.48 107.99 After 21 days at 23°C, 50% RH 61.99 89.55 After 28 days at 23°C, 50% RH 53.04 70.70 After 35 days at 23°C , 50% RH 51.59 67.61

After 20 hours in a water bath at 90 °C 22.85 22.62

Days at 100% hot creep (200 °C, 0.2 MPa) at 23 7 17 °C, 50% RH Days at 80% hot creep (200 °C, 0.2 MPa) at 23 10 25 °C, 50% RH

TABLE 6 - REGRESSION ANALYSIS FOR ““DAYS AT 100% HOT FLUENCE (200°C, 0.2 MPA) AT 23°C, 50% RH” Prob > |t|: The p value Statistically Coefficients associated with a significant test with 95% two-tailed confidence? Empirical Model 1 (R2 = 0.90) Intersect 3136.90 0.2551 NO Polydispersion - 21.96 0.0279 YES Density - 3252.10 0.2688 NO (Density - 0.91839) x - 9701.67 0. 0282 YES (Polydispersity - 6.60333) Empirical Model 2 (R2 = 0.95) Intersect 53.16 0.6945 NO Polydispersity - 11.77 0.1871 NO Amorphous Content at Temperature - 0.54 0.8686 NO Environment ( Amorphous Content at Ambient Temperature - 55.5178) x 9.21 0.0035 YES (Polydispersity - 6.6033)

TABLE 7 - REGRESSION ANALYSIS FOR “DAYS AT 80% HOT FLUENCE (200°C, 0.2 MPA) AT 23°C, 50% RH” Prob > |t|: The p value Statistically Coefficients associated with a significant test with 95% two-tailed confidence? Empirical Model 3 (R2 = 0.93) Intersect 7195.56 0.1723 NO Polydispersion - 49.03 0.0140 YES

54 / 54 Prob > |t|: Is the p-value Statistically Coefficients associated with a significant test with 95% two-tailed confidence? Density - 7,477.23 0.1833 NO (Density - 0.91839) x - 21,939.94 0.0135 YES (Polydispersity - 6.60333) Empirical Model 4 (R2 = 0.97) Intersect 73.75 0.7461 NO Polydispersion - 28.04 0.0834 NO Amorphous Content at Temperature 2.10 0.7027 NO Environment (Amorphous Content at Room Temperature - 55.5178) x 20.51 0.0010 YES (Polydispersity - 6.6033)

[00121] It will be evident to persons skilled in the art that various modifications and variations can be made to the modalities described in this document without departing from the spirit and scope of the claimed subject matter. Thus, it is intended that the descriptive report covers the modifications and variations of the modalities described in this document, provided that such modifications and variations are within the scope of the attached claims and their equivalents.

Claims (15)

1. Copolymer of hydrolyzable ethylene and silane, the copolymer being characterized in that it comprises one or both of 0.1% by weight to 5.0% by weight of hydrolysable silane groups and 0.02% by weight of 1.00 mol% of hydrolysable silane groups and has at least one of the following properties: an Mz(abs)/Mw(abs) less than or equal to 9.5; a ratio of Mz(abs)/Mw(abs) for polydispersity less than or equal to 1.5; a polydispersity of 6.6 or greater; an LCB of 2.9 or greater; a Density x Polydispersity of 6.0 or greater; an Amorphous Content at Room Temperature x Polydispersity” of 360 or greater; or an Amorphous Content at Ambient Temperature x Polydispersity x LCB of 1,000 or greater. 2. Copolymer according to claim 1, wherein the copolymer is characterized in that it comprises one or both of 0.9% by weight to 3.5% by weight of hydrolysable silane groups and 0.17% by mol to 0.68% by mol of hydrolysable silane groups. 3. Copolymer according to any one of claims 1 or 2, wherein the copolymer is characterized by the fact that it has at least one of the following properties: a Mz(abs)/Mw(abs) less than or equal to 9.0; a ratio of Mz(abs)/Mw(abs) for polydispersity less than or equal to 1.4; a polydispersity of 6.7 or greater; an LCB of 3.0 or greater; a Density x Polydispersity of 6.1 or greater; an Amorphous Content at Room Temperature x Polydispersity” of 370 or greater; or an Amorphous Content at Room Temperature x Polydispersity x LCB of 1100 or greater. 4. Copolymer according to any one of claims 1 or 2, wherein the copolymer is characterized by the fact that it has at least one of the following properties: a Mz(abs)/Mw(abs) less than or equal to 8.5; a ratio of Mz(abs)/Mw(abs) for polydispersity less than or equal to 1.3; a polydispersity of 7.0 or greater; an LCB of 3.1 or greater; a Density x Polydispersity of 6.5 or greater; an Amorphous Content at Room Temperature x Polydispersity of 400 or greater; or an “Ambient Temperature Amorphous Content x Polydispersity x LCB” of 1,200 or greater. 5. Polymeric composition crosslinkable by humidification, characterized in that it comprises: the copolymer, as defined in any one of claims 1 to 4; and a silanol condensation catalyst or catalyst masterbatch mixture or silanol condensation catalyst masterbatch. 6. Wet crosslinkable polymer composition according to claim 5, wherein the wetting crosslinkable polymer composition is characterized by the fact that it has a hot creep, measured at 0.2 MPa and 150 °C or 200 °C in extruded tape with a thickness of 50 mil (1.270 mm) to 80 mil (2.032 mm), less than or equal to 100% in 15 days or less than or equal to 80% in 23 days, where the tape produced from the crosslinkable polymeric composition by humidification it was cured at 23 ºC and 50% in relative humidity. 7. Wet crosslinkable polymer composition according to any one of claims 5 or 6, wherein the wetting crosslinkable polymer composition is characterized by the fact that it has a hot creep, measured at 0.2 MPa and 150 °C or 200 °C in extruded tape with a thickness of 30 mil (0.762 mm) to 80 mil (2.032 mm), less than or equal to 175% after curing the tape for 4 hours to 20 hours in a water bath at 90°C. 8. Wet crosslinkable polymeric composition according to any one of claims 5 to 7, characterized in that the copolymer of ethylene and hydrolyzable silane comprises from 10.00% by weight to 99.95% by weight of the polymeric composition crosslinkable by humidification, and the silanol condensation catalyst or catalyst masterbatch mixture or silanol condensation catalyst masterbatch comprises from 90.0% by weight to 0.05% by weight of the polymer composition crosslinkable by humidification. 9. Polymeric composition crosslinkable by humidification according to any one of claims 5 to 8, wherein the polymeric composition crosslinkable by humidification is characterized in that it further comprises one or more of: humidification removers or fire retardants; antioxidants; flame retardants; UV stabilizers and absorbers; metal deactivator; polyolefins without silane functionality; and silicones. 10. Cable, characterized by the fact that it comprises: a conductor; and an insulation or jacket that annularly surrounds the conductor, wherein the jacket comprises the wetting crosslinkable polymeric composition as defined in any one of claims 5 to 9. 11. Method for forming a crosslinkable polymer composition by humidification, characterized in that it comprises: forming a hydrolyzable copolymer of ethylene and silane at a polymerization temperature greater than or equal to 180 °C at less than or equal to 400 °C at a pressure of 5,000 psi (34.5 MPa) to 50,000 psi (344.7 MPa); and adding a silanol condensation catalyst to the copolymer of ethylene and hydrolyzable silane. 12. Method according to claim 11, characterized in that the copolymer of ethylene and hydrolyzable silane is formed at a polymerization temperature greater than or equal to 245°C to less than or equal to 325°C. 13. Method according to any one of claims 11 or 12, characterized in that the polymer composition crosslinkable by humidification has a hot creep, measured at 0.2 MPa and 150 °C or 200 °C in extruded tape with a thickness of 50 mil (1.270 mm) to 80 mil (2.032 mm), less than or equal to 100% in 15 days or less than or equal to 80% within 23 days, in which the tape produced from the polymer composition crosslinkable by humidification was cured at 23 ºC and 50% relative humidity. 14. Method according to any one of claims 11 to 13, characterized in that the polymer composition crosslinkable by humidification has a hot creep, measured at 0.2 MPa and 150 °C or 200 °C in extruded tape with a thickness of 30 mil (0.762 mm) to 80 mil (2.032 mm), less than or equal to 175% after curing the tape for 4 hours to 20 hours in a water bath at 90°C. 15. A method according to any one of claims 11 to 14, characterized in that the silanol condensation catalyst is added as a catalyst masterbatch mixture or silanol condensation catalyst masterbatch.